JP2022013902A - Olefin polymerization catalyst component, olefin polymerization catalyst, and method for producing olefin polymer - Google Patents

Abstract

[Problem] To provide a catalyst component for olefin polymerization capable of producing an olefin polymer having a sufficiently wide molecular weight distribution, the distribution being spread toward the high molecular weight side, and containing a sufficient amount of branched chains in the high molecular weight region of the molecular weight distribution. [Solution] The catalyst component for olefin polymerization combines, as component (I), a transition metal compound (metallocene complex) having a specific metallocene bridge structure and low comonomer copolymerization ability, and, as component (II), a specific transition metal compound having high comonomer copolymerization ability. [Selected Figure] None

Description

The present invention relates to an olefin polymerization catalyst component useful for producing an olefin polymer and a copolymer, an olefin polymerization catalyst containing the catalyst component, and an ethylene homopolymer or ethylene / ethylene using the olefin polymerization catalyst. The present invention relates to a method for producing an α-olefin copolymer.

Olefin polymers such as polyethylene and polypropylene are widely used as plastic molding materials. The olefin polymer as a molding material has moldability such as fluidity in a molten state, melt tension, and extensional viscosity, and molding such as hardness, rigidity, impact resistance, heat resistance, durability, and transparency after molding. Physical properties suitable for the purpose of the body are required.
Under these circumstances, the polyolefin produced by the metallocene catalyst for olefin polymerization has high uniformity of the polymer molecular structure such as molecular weight distribution and copolymer composition distribution, and is excellent in various mechanical properties such as impact strength and long life. Therefore, in recent years, the amount used has been increasing. However, although metallocene-based polyolefins are excellent in mechanical properties, they are inferior in important properties for molding of polyolefins such as melt tension and melt fluidity due to their narrow molecular weight distribution, and have sufficient performance in terms of molding. It didn't meet.

It is known to use a catalyst system in which two types of metallocene catalysts are combined for the purpose of improving the moldability and the physical properties of the olefin polymer after molding.
For example, Patent Document 1 discloses that a mixture of two types of metallocenes selected from a specific group of metallocene compounds is used as a method for producing a polyolefin having a wide molecular weight distribution and a high molecular weight.

Further, by copolymerizing ethylene and α-olefin, which is a comonomer, using a catalytic system in which two types of metallocene catalysts having different comonomer copolymerization abilities are combined, the molecular weight distribution and the amount of branched chains derived from α-olefin (the amount of branched chains derived from α-olefin) ( That is, attempts have been made to obtain an ethylene / α-olefin copolymer in which the amount of comonomer introduced) is adjusted.
For example, Patent Documents 2 to 4 describe only one type of metallocene by copolymerizing ethylene and comonomer with a metallocene having a low comonomer copolymerization ability and a metallocene having a high comonomer copolymerization ability using a combined catalytic system. Compared to ethylene / α-olefin copolymers produced using a catalyst, it has a wide multimodal molecular weight distribution and has many branched chains derived from comonomer in the high molecular weight side region of the molecular weight distribution. It is disclosed that the ethylene / α-olefin copolymer containing the mixture was obtained.

Patent Document 2 describes that ethylene and a comonomer are copolymerized by using a combination of a comonomer small amount uptake catalyst compound and a comonomer large amount uptake catalyst compound, but the former comonomer small amount uptake catalyst compound is relatively comonomer. It is a metallocene having a low polymerizable ability, and the latter catalyst compound having a large amount of comonomer uptake is a metallocene having a relatively high comonomer copolymerizable ability.
Patent Document 3 describes that a specific first metallocene compound and a specific second metallocene compound are used in combination to copolymerize ethylene and a comonomer. However, according to the description in paragraph 0006 of Patent Document 3. The former first metallocene compound is a metallocene having a relatively high comonomer copolymerization ability, and the latter second metallocene compound is a metallocene having a relatively low comonomer copolymerization ability.
Patent Document 4 describes that ethylene and comonomer are copolymerized by using two different components (, A) and component (B) selected from the group of group 4 metallocene compounds in the periodic table in combination. According to the description in paragraph 0020 of Patent Document 4, the former component (A) is a metallocene having a relatively low comonomer copolymerization ability, and the latter component (B) is a metallocene having a relatively high comonomer copolymerization ability. Is.

In addition, Non-Patent Document 1 describes an experiment in which homopolymers of ethylene and propylene were synthesized using dichloro {o-phenylenedimethylenebis (η5-1-indenyl) zirconium}, which is one of the crosslinked metallocenes. Are listed.

Japanese Patent Application Laid-Open No. 7-179512 JP-A-2007-284691 Special Table 2009-504901 JP-A-2010-202791

Macromolecules, 1995, vol.28, p.4801

In the technique of controlling the molecular weight distribution and the comonomer composition distribution using a plurality of transition metal compounds, the molecular weight distribution is used in order to produce an olefin-based polymer having an excellent balance between formability and rigidity, strength and durability. There is a need for a catalyst for olefin polymerization that can increase the amount of comonomer introduced on the high molecular weight side by selectively introducing the comonomer on the high molecular weight side of the molecular weight distribution.
However, as will be described later, the metallocene catalysts disclosed in Patent Documents 2 to 4 cannot always sufficiently satisfy the above technical requirements.
Further, Non-Patent Document 1 does not describe anything about the copolymerization ability of dichloro {o-phenylenedi methylenebis (η5-1-indenyl) zirconium} in the case of copolymerizing ethylene and α-olefin.

In contrast to the prior art as described above, the present invention has a sufficiently wide molecular weight distribution, a distribution on the high molecular weight side, and an olefin-based weight containing a sufficient amount of branched chains in the high molecular weight side region of the molecular weight distribution. It is an object of the present invention to provide a catalyst component for olefin polymerization capable of producing a coalescence.
Another object of the present invention is to provide a method for producing an ethylene-based polymer having an excellent balance between formability and rigidity, strength and durability by using the above-mentioned catalyst component for olefin polymerization. ..

As a result of diligent studies to solve the above problems, the present inventor has obtained a transition metal compound (metallocene complex) having a specific metallocene crosslinked structure and a low comonomer copolymerization ability, and a specific transition metal compound having a high comonomer copolymerization ability. By using a catalyst containing a combined catalyst component, the molecular weight distribution is sufficiently wide, the distribution is widened on the high molecular weight side, and the olefin-based weight containing a sufficient amount of branched chains in the high molecular weight side region of the molecular weight distribution. We have found that a coalescence can be obtained, and have completed the present invention.

That is, the catalyst component for olefin polymerization of the present invention is a catalyst component characterized by containing the following components (I) and (II).
[Component (I)]
Transition metal compound represented by the following formula (1)

[During the ceremony,
M ¹ represents a transition metal of Group 4 of the periodic table.
L ¹ and L ² represent a ligand containing a cyclopentadienyl structure and are coordinated to M ¹ .
Each of X ¹ and X ² independently has a hydrogen atom, a halogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon containing an oxygen atom or a nitrogen atom. A hydrocarbon group having a number of 3 to 20 or a hydrocarbon group substituted amino group having a carbon number of 1 to 20 is shown.
J ¹ and J ² represent carbon atoms.
A ¹ and A ² indicate a cross-linking group that binds J ¹ and L ¹ and J ² and L ² , respectively, and are selected from the following groups.
-CR ³ _2- , -SiR ³ _2- , -NR ^3- , -PR ^3- , -O-, -S-, [Here, R ³ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Two ^R3s may combine to form a cyclic structure],
R ¹ and R ² independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a hydrocarbon having 1 to 20 carbon atoms including 1 to 6 silicon atoms. A hydrogen group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms is shown. R ¹ and R ² may combine with each other to form a cyclic structure with J ¹ and J ² . ]

[Ingredient (II)]
Transition metal compound selected from the compound group represented by the following formula (2), formula (3) or formula (4) A ³ _q L ³ L ^{3'M 3} X ³ X ^3'formula (2)
[During the ceremony,
M ³ indicates a transition metal of Group 4 of the periodic table.
L ³ and L ^{3'independently} represent ligands containing a cyclopentadienyl structure and are coordinated to M ³ . The ligand containing the cyclopentadienyl structure has a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms containing 1 to 6 silicon atoms. Substituted with a hydrocarbon group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group substituted silyl group having 1 to 20 carbon atoms. It may have been. If adjacent substituents are present on L ³ or L ^3' , they may be combined to form a ring structure.
X ³ and X ^3'contain a hydrogen atom ^, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom independently of each other. A hydrocarbon group having 3 to 20 carbon atoms or a hydrocarbon group substituted amino group having 1 to 20 carbon atoms is shown.
A ³ indicates a cross-linking group that crosslinks L ³ and L ^3' , and may or may not be present, and if present, has a cross-linking structure between L ³ and L ^3' .
q is 0 or ¹ and indicates the number of A3. ]

Equation (3):
A ⁴ L ⁴ M ⁴ X ⁴ X ^4'
[During the ceremony,
M ⁴ indicates a transition metal of Group 4 of the periodic table.
L ⁴ represents a ligand containing a cyclopentadienyl structure and is coordinated to M ⁴ . The ligand containing the cyclopentadienyl structure has a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms containing 1 to 6 silicon atoms. Substituted with a hydrocarbon group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group substituted silyl group having 1 to 20 carbon atoms. It may have been.
^X4 and ^{X4'independently} form a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom, which are bonded to the metal ^M4 , respectively. A hydrocarbon group having 3 to 20 carbon atoms or a hydrocarbon group substituted amino group having 1 to 20 carbon atoms is shown.
A ⁴ represents an organic group having a hetero atom bonded to L ⁴ , and is bonded to M ⁴ via the hetero atom. ]

Equation (4):
L ⁵ _m M ⁵ X ⁵ _p
[During the ceremony,
M ⁵ indicates a transition metal of Group 3 to 11 of the Periodic Table.
The m ^L5s each independently represent a hydrocarbon group substituted with a substituent having an atom selected from two or more oxygen, nitrogen, phosphorus, and sulfur atoms, and at least two of the oxygen. , Nitrogen, phosphorus, and an atom selected from sulfur atoms are bonded to ^M5 .
Each of the p X ^5s independently has a hydrogen atom, a halogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon containing an oxygen atom or a nitrogen atom. The number 3 to 20 hydrocarbon groups or neutral Lewis bases are shown.
m represents the number of L5 and is ¹ or 2.
p indicates the number of X, which is the number selected so that the transition metal compound of the formula (4) is electrically neutral. ]

Further, the olefin polymerization catalyst of the present invention comprises the following components (I), component (II), component (III) and component (IV), and the olefin polymerization catalyst and the following components ( I), a catalyst for olefin polymerization produced by mixing the component (II), the component (III) and the component (IV).
[Component (I)]
Transition metal compound represented by the above formula (1) [Component (II)]
A transition metal compound selected from the compound group represented by the above formula (2), formula (3) or formula (4) [Component (III)]
A compound that reacts with a transition metal compound of component (I) and component (II) to form a cationic compound [component (IV)].
Fine particle carrier

Further, the method for producing an ethylene-based polymer of the present invention is characterized in that the copolymerization of an α-olefin selected from the group consisting of ethylene and an α-olefin other than ethylene is carried out using the above-mentioned olefin polymerization catalyst of the present invention. do.

According to the present invention, it is possible to produce an olefin-based polymer having a sufficiently wide molecular weight distribution, a wide distribution on the high molecular weight side, and a sufficient amount of branched chains in the high molecular weight side region of the molecular weight distribution. It is possible to provide a catalyst component for olefin polymerization that can be produced.
Further, it is possible to provide a catalyst for olefin polymerization containing this catalyst component, and a method for producing an olefin polymer using this catalyst, particularly a method for producing an ethylene-based polymer.

FIG. 1 is the result of GPC-IR of polyethylene obtained in Example 1. FIG. 2 shows the results of GPC-IR of polyethylene obtained in Example 4. FIG. 3 shows the results of GPC-IR of polyethylene obtained in Example 7.

Hereinafter, the present invention will be described.
In the present invention, "polymerization" is a general term for homopolymerization of one type of monomer and copolymerization of a plurality of types of monomers, and when it is not necessary to distinguish between the two, the generic term is simply "polymerization". It is described as "polymerization".
Further, in the present invention, "-" indicating a numerical range is used in the sense that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
In the present invention, "Ph" stands for phenyl, "Me" stands for methyl or methyl group, "Et" stands for ethyl or ethyl group, "Pr" stands for propyl or propyl group, and "Hex" stands for hexyl or hexyl group. Further, "i" associated with the alkyl group name represents iso, "n] represents normal, "t" represents tertiary, and "c" represents cycloisomeric structure. If the alkyl group is not accompanied by an isomer structure, it indicates that it has a normal structure.

I. Catalyst component for olefin polymerization The catalyst component for olefin polymerization of the present invention is a component (I) which is a transition metal compound represented by the formula (1) described later, and the formula (2), the formula (3) or the formula described later. It is a catalyst component for olefin polymerization, which comprises a component (II) which is a transition metal compound selected from the compound group represented by (4). In the comparison between the component (I) and the component (II), the component (I) is a transition metal compound having a relatively low copolymerization ability, and the component (II) is a transition metal compound having a relatively high copolymerization ability. , Both transition metal compounds have catalytic activity for olefin polymerization.
The catalyst component for olefin polymerization of the present invention has a sufficiently wide molecular weight distribution, a wide distribution on the high molecular weight side, and an olefin polymer containing a sufficient amount of branched chains in the high molecular weight side region of the molecular weight distribution. It is useful as a catalytically active component of a catalyst for olefin polymerization that can be produced. The catalyst component for olefin polymerization of the present invention can be combined with a co-catalyst or a carrier to obtain a catalyst for olefin polymerization.

In the technique of controlling the molecular weight distribution and the comonomer composition distribution using a plurality of transition metal compounds, the molecular weight distribution is used in order to produce an olefin-based polymer having an excellent balance between formability and rigidity, strength and durability. There is a need for a catalyst for olefin polymerization that can increase the amount of comonomer introduced on the high molecular weight side by selectively introducing the comonomer on the high molecular weight side of the molecular weight distribution.

In Table 1 and paragraphs 0035 to 0036 of Patent Document 2, ethylene and hexencomonomer are contained in a comonomer small amount uptake catalytic compound (that is, metallocene having a low comonomer copolymerization ability) or a comonomer large amount uptake catalytic compound (that is, a comonomer copolymerizable ability). For some ethylene-hexene copolymers obtained by copolymerizing in a vapor phase process using (high metallocene) alone, with varying hexene / ethylene ratios (C6 / C2) and the same other conditions. , The relationship between hexene / ethylene ratio and density, melt index (MI) and MFR is shown.
In general, when an olefin is copolymerized using metallocene having a low comonomer copolymerization ability, the comonomer cannot be sufficiently introduced unless the comonomer / monomer ratio of the charged monomer is high, while the comonomer copolymerizability is high. When the olefin is copolymerized with a high metallocene, the comonomer can be sufficiently introduced even if the comonomer / monomer ratio of the charged monomer is low.
If metallocene having a low comonomer copolymerization ability and metallocene having a high comonomer copolymerization ability are used alone, copolymerization is carried out under the same polymerization conditions other than the comonomer / monomer ratio of the charged monomer, and the same density is obtained. When obtaining a polymer, it is necessary to increase the comonomer / monomer ratio of the charged monomer as the copolymerization ability of the comonomer of metallocene is lower.
That is, when the copolymers obtained by using two different metallocenes are compared with each other having the same density, that is, in terms of density, the hexene / ethylene ratio of the charged monomer at the time of polymerization is large. The lower the copolymerization ability of the metallocene used, the lower the copolymerization ability of the comonomer of the metallocene used, while the smaller the hexene / ethylene ratio of the charged monomer at the time of polymerization, the higher the copolymerization ability of the comonomer of the metallocene used.

In paragraph 0036 of Patent Document 2, the molar ratio of comonomer / monomer required for the comonomer small amount incorporated catalyst of the catalyst to produce a polymer having a density of 0.920 g / cc is as follows. It is preferably at least 2 times the value of the molar ratio of comonomer / monomer required to make the polymer of, 3 times is more preferable, 4 times is more preferable, and 5 times is even more preferable. It is stated that it is preferable.
According to the data shown in Table 1 of Patent Document 2, the hexene / ethylene ratio of the charged monomer of the copolymer obtained by using the comonomer small amount uptake catalyst and the copolymer obtained by using the comonomer large amount uptake catalyst. When comparing the hexene / ethylene ratio of the charged monomer in terms of density, the one with the largest hexene / ethylene ratio among the examples of use of the comonomer small amount uptake catalyst and the one with the largest use example of the comonomer large amount uptake catalyst. The ratio to the one having a small hexene / ethylene ratio is about 10 times (for example, the molar ratio of C6 / C2 in the Meso-O (Me ₂ SiIND) ₂ complex described in the 8th row of Table 1 of Patent Document 2 is An example showing a density of 0.934 at 0.056 and an example showing a density of 0.929 at a molar ratio of C6 / C2 in the MeSi (H ₄ IND) ₂ complex described in line 35 of the same table of 0.005. When comparing.). However, there is no description of an experiment in which a copolymer is actually combined with a comonomer small amount uptake catalyst and a comonomer large amount uptake catalyst so that the copolymerization ability ratio is about 10 times.
Further, in Example 5C of Patent Document 2, the molecular weight distribution (Mw / Mn) of the ethylene-hexene copolymer obtained by using the comonomer small amount uptake catalyst and the comonomer large amount uptake catalyst in combination is about 3.5 to 4. It is stated that the value was 5, and it cannot be said that the molecular weight distribution is sufficiently wide from the viewpoint of moldability.

In Patent Document 3, the copolymerization ability when the first metallocene compound (that is, metallocene having high comonomer copolymerization ability) is used alone and the second metallocene compound (that is, metallocene having low comonomer copolymerization ability) are used alone. The difference in copolymerizability, that is, the reactivity ratio, is not clearly described.
However, referring to the GPC-IR data shown in FIG. 2 of Patent Document 3, the number of short-chain branched chains in the polymer at the low molecular weight side peak obtained by using the second metallocene compound alone and the first metallocene. It is estimated that the ratio of the number of short-chain branched chains in the polymer at the polymer-side peak obtained by using the compound alone is about 3 times.

Table 5 of Patent Document 4 shows the number of short chain branches (1/1000 C, when the components (A-1) to (A-5) (that is, metallocene having a relatively low comonomer copolymerizable ability) are used alone. The number of short-chain branches per 1000 carbon atoms) and the number of short-chain branches when the components (B-1) to (B-2) (that is, metallocene having a relatively high comonomer copolymerization ability) are used alone. (1/1000C) is shown, and the smallest number of short-chain branches of the low molecular weight component obtained by using the components (A-1) to (A-5) alone, and the components (B-1) to (B-1) to ( The difference in the number of short-chain branches having the largest molecular weight component obtained by using B-2) alone, that is, the ratio is about 5.5 times.

In contrast to the above-mentioned prior art, in the present invention, the catalyst component is a combination of the above component (I) as a transition metal compound having a low copolymerization ability and the above component (II) as a transition metal compound having a high copolymerization ability. The olefin main monomer and the olefin comonomer are copolymerized using a catalyst for olefin polymerization containing the above. By this polymerization reaction, a copolymer having a small molecular weight and a low comonomer content is synthesized by a catalytic reaction mediated by the component (I) in one reaction system, and at the same time, a catalytic reaction mediated by the component (II). A copolymer having a large molecular weight and a high comonomer content is synthesized. As a result, a large amount of the copolymer having a low comonomer content generated by the catalytic reaction mediated by the component (I) is contained on the low molecular weight side, while the comonomer content generated by the catalytic reaction mediated by the component (II) is contained. An olefin-based polymer containing a large amount of a large amount of copolymer on the high molecular weight side can be obtained.
Therefore, when looking at the reaction system as a whole, an olefin polymer is produced that has a sufficiently wide molecular weight distribution, a distribution on the high molecular weight side, and a sufficient amount of branched chains in the high molecular weight side region of the molecular weight distribution. be able to.
In particular, the catalyst component in which the above component (I) and the above component (II) are combined has a feature that the difference between the comonomer content on the low molecular weight side and the comonomer content on the high molecular weight side can be made larger than that of the conventional catalyst. be.

The reason why component (I) produces a polymer with a low comonomer content is that the two ligands (L ¹ , L ² ) of component (I) bind to bridging groups (A ¹ , A ² ) and are specific. Since the chemical structure (-L ¹ -A ¹ -J ¹ = J ² -A ² -L ^2- ) is taken, these two ligands (L ¹ , L ² ) are coordinated to the central metal (M ¹ ). It is considered that this is because the substituent on the ligand has a structure in which the monomer is extruded in the direction of coordination. However, when the ligand is indenyl, the condensed ring portion having 4 carbon atoms fused to the 5-membered ring protrudes in the direction in which the monomer is coordinated, considering the 5-membered ring as a reference. It is thought to take. In a specific chemical structure (-L ¹ -A ¹ -J ¹ = J ² -A ² -L ^2- ), J ¹ = J ² takes an SP2 hybrid orbital and the cross-linking group (A ¹ , A ² ) is sp3. When connected by a hybrid orbital of, the right angle and distance are established, and the above-mentioned protrusion is possible.
If there is an obstacle in the direction in which the monomer is coordinated in this way, it becomes difficult to coordinate the larger comonomer, so the monomer such as ethylene coordinates to the central metal and changes to a polymer. Such comonomer is less likely to be incorporated into the polymer.
In order to further facilitate the above-mentioned structure, when the ligand (L ¹ , L ² ) is indenyl, the cross-linking group (A ¹ , A ² ) is located at the position 1 or 3 of the indenyl. It is preferable that it is bound to.

As described above, by combining a metallocene having a low copolymerization ability having a bond distance and an angle due to a specific crosslinked portion as a component (I) with a transition metal compound having a high copolymerization ability which is a component (II). , The difference between the comonomer content on the low molecular weight side and the comonomer content on the high molecular weight side in the copolymer can be increased. As the component (II), a transition metal compound having a copolymerizable ability and a high molecular weight is used, but a crosslinked bisinden type, a crosslinked cyclopentadiene-fluorene type, and a crosslinked bisfluorene type are preferably used. The cross-linking group in this case is preferably silicon or a carbon atom. It is believed that the cross-linking group widens the dihedron angle of the two surfaces formed by the 5-membered ring portions of the two ligands, eliminating the obstacles to coordination of the comonomer and increasing the reactivity with the comonomer.
Various combinations of ligands can be considered for the ligand, and among the ligands having a cyclopentadienyl structure, those having a high molecular weight are preferably bisindene, cyclopentadiene-fluorene, or bisfluorene type.

The difference between the comonomer content on the low molecular weight side and the comonomer content on the high molecular weight side can be evaluated by any of the following methods.
Method 1:
The molecular weight distribution curve of the olefin polymer and the correlation curve between the molecular weight of the polymer contained in the olefin polymer and the number of branches derived from the comonomer are superimposed on a single graph with the molecular weight as a common axis, and the molecular weight distribution is distributed. The low molecular weight side region and the high molecular weight side region are separated from the shape of the curve, and the number of branches existing in the low molecular weight side region and the number of branches existing in the high molecular weight side region are compared. In this method, the number of branches at the low molecular weight side peak of the molecular weight distribution curve may be compared with the number of branches at the high molecular weight side peak of the molecular weight distribution curve.
Method 2:
One cumulative curve of the number of branches derived from the comonomer obtained from the correlation curve between the molecular weight distribution curve of the olefin polymer and the molecular weight of the polymer contained in the olefin polymer and the number of branches derived from the comonomer. By superimposing the molecular weights on the common axis on the graph, the low molecular weight side region and the high molecular weight side region are separated from the shape of the molecular weight distribution curve, and the gradient of the cumulative number of branches from the low molecular weight side to the high molecular weight side (radicality) is observed. do.
Method 3:
A polymerization catalyst containing the component (I) but not the component (II) and a polymerization catalyst containing the component (II) but not the component (I) are used independently, and the olefin is copolymerized under the same polymerization conditions. By doing so, a low-molecular-weight copolymer is obtained from the component (I), which is a transition metal compound having a low copolymerization ability, while a high-molecular-weight copolymer is obtained from the component (I), which is a transition metal compound having a high copolymerization ability. Is produced, and the number of branches contained in the low molecular weight copolymer is compared with the number of branches contained in the high molecular weight copolymer.

Although the description is merely an example belonging to the present invention, according to the present invention, the olefin polymer has a molecular weight distribution (Mw / Mn) of 6 or more and 60 or less, and at the same time, the above method 3 is used. The ratio of the high molecular weight side comonomer content (high molecular weight side comonomer content / low molecular weight side comonomer content) to the low molecular weight side comonomer content specified by 4 times or more, further 8 times or more, and further 10 times. The above can be done.

Hereinafter, the component (I) and the component (II) will be described.
In the present specification, for example, "a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom" and "a hydrocarbon group having 1 to 20 carbon atoms including 1 to 6 silicon atoms". In some cases, the description "a hydrocarbon group having a number of carbon atoms a to b including a heterogeneous atom X such as an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom" may be used.
In this case, the "hydrocarbon group containing a heteroatom X" means that a heteroatom X having no bond with a hydrogen atom or having only a bond with a carbon atom exists on or in the carbon chain of the hydrocarbon group. It means that you are doing.
For example, when a heterologous atom having only a bond with a carbon atom is present on the carbon chain of the hydrocarbon group, an alkoxy group, a thioether group, a dialkylamino group or a trialkylsilyl group is bonded to the end of the alkyl group. This may be the case, the case where the alkyl group is bonded in the middle of the alkyl group, or the case where the oxo group is bonded to the end or the middle of the alkyl group.
Further, "existing in the carbon chain of the hydrocarbon group" means a state in which the carbon chain of the hydrocarbon group is interrupted by a heteroatom.
For example, examples of the presence in the carbon chain of the hydrocarbon group include a case where an ether bond or a thioether bond is inserted in the middle of the chain hydrocarbon group, and a case where the structure is a cyclic ether.
Further, in this case, the carbon number of the hydrocarbon group containing a heteroatom means the number of carbon atoms contained in the entire hydrocarbon group containing a heteroatom. For example, the "hydrocarbon group having a number of carbon atoms a to b containing a heteroatom" means that the total number of carbon atoms including the carbon atom of the carbon chain divided by the heteroatom in the hydrocarbon group is a to b. Means. More specifically, the methoxymethyl group (CH ₃ O-CH _2- ) has 2 carbon atoms.

1. 1. Ingredient (I)
The component (I) used in the present invention is a transition metal compound represented by the following formula (1).

[During the ceremony,
M ¹ represents a transition metal of Group 4 of the periodic table.
L ¹ and L ² represent a ligand containing a cyclopentadienyl structure and are coordinated to M ¹ .
Each of X ¹ and X ² independently has a hydrogen atom, a halogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon containing an oxygen atom or a nitrogen atom. A hydrocarbon group having a number of 3 to 20 or a hydrocarbon group substituted amino group having a carbon number of 1 to 20 is shown.
J ¹ and J ² represent carbon atoms.
A ¹ and A ² indicate a cross-linking group that binds J ¹ and L ¹ and J ² and L ² , respectively, and are selected from the following groups.
-CR ³ _2- , -SiR ³ _2- , -NR ^3- , -PR ^3- , -O-, -S-, [Here, R ³ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Two ^R3s may combine to form a cyclic structure],
R ¹ and R ² independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a hydrocarbon having 1 to 20 carbon atoms including 1 to 6 silicon atoms. A hydrogen group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms is shown. R ¹ and R ² may combine with each other to form a cyclic structure with J ¹ and J ² . ]

M ¹ is a transition element of Group 4 of the periodic table. As M ¹ , for example, a titanium atom (Ti), a zirconium atom (Zr), or a hafnium atom (Hf) is used, but the zirconium atom has a lower copolymerization ability and a higher polymerization activity than the hafnium atom. A zirconium atom is preferred because it can be used.

L ¹ and L ² contain a cyclopentadienyl structure and are ligands that coordinate to M ¹ . Examples of the ligand containing a cyclopentadienyl structure include a ligand having a cyclopentadienyl skeleton, a ligand having an indenyl skeleton, and a ligand having a fluorenyl skeleton. The ligand containing the cyclopentadienyl structure may have a part of the unsaturated bond contained in the skeleton substituted with a hydrogen atom. For example, the ligand having an indenyl skeleton is a tetrahydroindenyl group. You may. Further, L ¹ and L ² may be different such as cyclopentadienyl skeleton and indenyl skeleton, cyclopentadienyl skeleton and fluorenyl skeleton, and indenyl skeleton and fluorenyl skeleton, respectively.
The ligand containing the cyclopentadienyl structure may have a substituent. In particular, in the case of a ligand having a cyclopentadienyl skeleton, it is preferably two substitutions or more. Examples of the substituent include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including 1 to 6 silicon atoms, and a hydrocarbon group having 1 to 20 carbon atoms. Examples thereof include a halogen-substituted hydrocarbon group having 1 to 20, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms. If adjacent substituents are present on L ¹ or L ² , they may be combined to form a ring structure. Further, the position of the substituent on L ¹ or L ² is arbitrarily selected, and in the case of the indenyl skeleton, the 1-substituted type at the 2-position, 3-position and 4-position, and the 2-substituted type at the 4, 7 and 5, 6 positions. Can be mentioned.

Specific examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.
Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and a t-butyl group. , N-pentyl group, neopentyl group, n-hexyl group, octyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and other alkyl groups or cycloalkyl groups; vinyl group, propenyl group, butenyl group, hexenyl group, cyclohexenyl group Alkenyl groups such as; alkyl groups having alicyclic substituents such as cyclopentylmethyl group and 2-cyclohexylethyl group; phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3,5 -Dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-t-butylphenyl group, 3,5-di-t-butylphenyl group, 4-vinylphenyl group, 3-allylphenyl group, 4-( 3-Butenyl) A monocyclic or fused ring aryl group that may be substituted with a saturated or unsaturated hydrocarbon group such as a phenyl group or a naphthyl group; an aromatic substituent such as a benzyl group or a 2-phenylethyl group. Examples thereof include an alkyl group having.

Specific examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a t-butoxy group, a phenoxy group and the like. be able to.
Specific examples of a hydrocarbon group having 1 to 20 carbon atoms containing 1 to 6 silicon atoms include a hydrocarbon group substituted with 1 to 6 trialkylsilyl groups and containing a carbon atom of the alkylsilyl group. Hydrocarbon groups having a total number of carbon atoms of 1 to 20 can be mentioned. More specifically, an alkylsilyl substituted alkyl group such as a bis (trimethylsilyl) methyl group, a bis (t-butyldimethylsilyl) methyl group, a trimethylsilylethyl group, a triethylsilylethyl group, a 2-trimethylsilylpropyl group; 4-trimethylsilylphenyl. Examples thereof include an alkylsilyl substituted aromatic hydrocarbon group such as a group.

Specific examples of the halogen-substituted hydrocarbon group having 1 to 20 carbon atoms include a bromomethyl group, a chloromethyl group, a trifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 2,2,2-trifluoroethyl group, and the like. Alkyl halides such as 2-bromopropyl group, 3-bromopropyl group, 3,3,3-trifluoropropyl group, 4-chlorobutyl group, 3-fluorobutyl group, 4,4,4-trifluorobutyl group , 2-bromocyclopentyl group, 2,3-dibromocyclopentyl group, 2-bromo-3-iodocyclopentyl group, 2,3-dibromocyclohexyl group, 2-chloro-3-iodocyclohexyl group and other halide cycloalkyl groups, Halogenized aromatic groups such as 2-chlorophenyl group, 4-chlorophenyl group, 3,5-dichlorophenyl group, 2,3,4,5,6-pentafluorophenyl group, halogenation of 4-trifluoromethylphenyl group and the like. Alkyl aromatic groups and the like can be mentioned.

Specific examples of the hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom are as follows. As those containing oxygen, ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, t-butoxymethyl group, methoxyethyl group, ethoxyethyl group, 4- Ekalkyl fragrances such as alkoxyalkyl groups such as methoxybutyl group, 3-ethoxybutyl group and 6-methoxyhexyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group and 2,4-dimethoxyphenyl group. Group group, acetyl group, 1-oxopropyl group, 1-oxo-n-butyl group, 2-methyl-1-oxopropyl group, 2,2-dimethyl-1-oxo-propyl group, phenylacetyl group, diphenylacetyl Oxo group-containing hydrocarbon groups such as groups and benzoyl groups, cyclic ether groups such as 2-furyl groups, 2-tetrahydrofuryl groups and 2-methylfuryl groups; 2-thienyl groups and 2-thienyl groups as those containing a sulfur atom. Tetrahydrothienyl group, 2-methylthienyl group, etc .; and dimethylaminomethyl group, diethylaminomethyl group, di-propylaminomethyl group, bis (dimethylamino) methyl group, bis (dii-) as those containing a nitrogen atom. Propylamino) methyl group, (dimethylamino) (phenyl) methyl group, aminoethyl group, dimethylaminoethyl group, diethylaminoethyl group, 1- (methylimino) ethyl group, 1- (phenylimino) ethyl group, 1-[( Phenylmethyl) imino] Amino-substituted alkyl groups such as ethyl group and dimethylaminohexyl group, amino-substituted aromatic groups such as 4-aminophenyl group and 4-dimethylaminophenyl group can be mentioned.

Specific examples of the hydrocarbon group substituted silyl group having 1 to 20 carbon atoms include an alkylsilyl group such as a trimethylsilyl group, a trit-butylsilyl group, a dit-butylmethylsilyl group and a t-butyldimethylsilyl group, and a triphenylsilyl. Examples include an aromatic silyl group such as a group, a diphenylmethylsilyl group, and a phenyldimethylsilyl group.

Each of X ¹ and X ² independently has a hydrogen atom, a halogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon containing an oxygen atom or a nitrogen atom. It is a hydrocarbon group having 3 to 20 carbon atoms or a hydrocarbon group substituted amino group having 1 to 20 carbon atoms.
As a specific example of the halogen atom, specific examples of the halogen atom described for the substituents of L ¹ and L ² can be given for X ¹ and X ² .
As specific examples of the hydrocarbon groups having 1 to 20 carbon atoms, specific examples of the hydrocarbon groups having 1 to 20 carbon atoms described above for the substituents of L ¹ and L ² are also given for X ¹ and X ² . Can be done.
As a specific example of the alkoxy group having 1 to 20 carbon atoms, specific examples of the alkoxy group having 1 to 20 carbon atoms described for the substituents of L ¹ and L ² can be given also for X ¹ and X ² . ..
As a specific example of the hydrocarbon group having 3 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, the hydrocarbon group having 3 to 20 carbon atoms containing an oxygen atom or a nitrogen atom described above for the substituents of L ¹ and L ² has been described. Specific examples of X ¹ and X ² can also be given.
Specific examples of the hydrocarbon group-substituted amino group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a din-propylamino group, a di-butylamino group, a dit-butylamino group, and a diphenylamino group. Can be mentioned.

J ¹ and J ² represent carbon atoms. When J ¹ and J ² are bonded by a double bond and J ¹ and J ² become sp2 hybrid orbitals, the ligands L ¹ and L ² are transition metals in cooperation with the bridging groups A ¹ and A ² . It can be coordinated to M ¹ at an appropriate angle. A carbon atom is optimal at the positions of J ¹ and J ² as an atom capable of coordinating the ligands L ¹ and L ² to the transition metal M ¹ at an appropriate angle.

A ¹ and A ² are cross-linking groups that bind J ¹ and L ¹ and J ² and L ² , respectively, and are selected from the following groups: -CR ³ _2- , -SiR ³ _2- , -NR ³ -, -PR ^3- , -O-, -S-, [Here, R ³ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and two R ^3s are bonded to form a cyclic structure. May be good].
As specific examples of the hydrocarbon groups having 1 to 10 carbon atoms which are R3 ^, among the specific examples of the hydrocarbon groups described for the substituents of L1 and L2, those having ¹ to ¹⁰ carbon atoms ^are also used for R3. Can be mentioned.
As A ¹ and A ² , a methylene group having an unsubstituted or alkyl group having 1 to 4 carbon atoms and a silylene group having an unsubstituted or alkyl group having 1 to 4 carbon atoms are preferable.

R ¹ and R ² independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a hydrocarbon having 1 to 20 carbon atoms including 1 to 6 silicon atoms. It is a hydrogen group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms.

As specific examples of the hydrocarbon groups having 1 to 20 carbon atoms, specific examples of the hydrocarbon groups having 1 to 20 carbon atoms described above for the substituents of L ¹ and L ² are also given for R ¹ and R ² . Can be done.
As a specific example of the alkoxy group having 1 to 20 carbon atoms, specific examples of the alkoxy group having 1 to 20 carbon atoms described above for the substituents of L ¹ and L ² can be given for R ¹ and R ² . ..
As a specific example of the hydrocarbon group having 1 to 20 carbon atoms containing 1 to 6 silicon atoms, 1 to 20 carbon atoms containing 1 to 6 silicon atoms described above for the substituents of L ¹ and L ² have been described. Specific examples of the hydrocarbon group of R ¹ and R ² can also be mentioned.
As specific examples of the halogen-substituted hydrocarbon groups having 1 to 20 carbon atoms, the specific examples of the halogen-substituted hydrocarbon groups having 1 to 20 carbon atoms described above for the substituents L ¹ and L ² are R ¹ and R ² . Can also be mentioned.
As a specific example of the hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, the carbon number 3 containing an oxygen atom, a sulfur atom or a nitrogen atom described above for the substituents of L ¹ and L ² Specific examples of the hydrocarbon groups of about 20 can be given for R ¹ and R ² .
As a specific example of the hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, the specific example of the hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms described with respect to the substituents of L ¹ and L ² is referred to as ^R1 . ^R2 can also be mentioned.

When R ¹ and R ² and J ¹ and J ² form a part of the cyclic structure together, the cyclic structure may be, for example, benzene-1,2-diyl group, naphthalene-2,3-diyl group, phenanthrene-. Aromatic rings such as 9,10 diyl groups, cyclobutane-1,2-diyl group (cyclobutylidene group), cyclopentane-1,2-diyl group (cyclopentylidene group), cyclohexane-1,2- A 4- to 7-membered ring composed of carbon atoms such as a diyl group (cyclohexylidene group); bicyclo [2.2.1] heptane-diyl group (norbornane-diyl group), bicyclo [4.4.0] decan. -An alicyclic bicyclo ring such as a diyl group (decalin-diyl group) can be mentioned.
These cyclic structures may contain a double bond other than the double bond between J ¹ and J ² on the ring skeleton, or an alkyl group, a hydrocarbon group such as alkenyl, a halogen, etc. on the ring skeleton. It may have other substituents. Further, this cyclic structure may have a crosslinked structure for cross-linking between the atoms forming the ring skeleton.

Furthermore, if there are two or more substituents on the ring skeleton containing R ¹ and R ² and J ¹ and J ² , those substituents bind to each other to close the ring, and R ¹ and R ² and J ¹ and A condensed polycyclic structure may be formed that shares a part of the constituent atoms of the ring skeleton containing J ² .
Ring skeletons containing R ¹ and R ² and J ¹ and J ² and fused rings containing other ring skeletons have substituents on ring skeletons other than those containing R ¹ and R ² and J ¹ and J ² . You may have. Examples of the substituent on the fused ring include an alkyl group, a hydrocarbon group such as alkenyl, and a halogen.
Examples of the annular structure formed by R ¹ and R ² and J ¹ and J ² include structures a to n below.

Among the compounds represented by the above formula (1), the compounds represented by any of the following formulas (1-1) to (1-5) are preferable.
Formulas (1-1) to (1-5) are 6-membered rings including R ¹ and R ² and J ¹ and J ² in which R ¹ and R ² are coupled to each other to form a ring closure in the formula (1). It is a compound forming a cyclic structure of.

[During the ceremony,
M ¹ , L ¹ , L ² , X ¹ , X ² , J ¹ , J ² , A ¹ and A ² are the same as those in the above formula (1).
^R4 indicates a substituent existing on the 6-membered ring, and may or may not be present. If present, each of them independently has a halogen atom, a hydrocarbon group having 1 to 9 carbon atoms, and carbon. An alkoxy group having a number of 1 to 9, a halogen-substituted hydrocarbon group having 1 to 9 carbon atoms, a hydrocarbon group having 3 to 9 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, and a hydrocarbon group having 1 to 9 carbon atoms. It is an amino group that may be substituted with a silyl group or a hydrocarbon group having 1 to 9 carbon atoms. R ⁴ may form a crosslinked structure in the 6-membered ring in which the R ⁴ is present. When two or more R ^4s are present, they may be bonded to form a fused ring that shares a part of the constituent atoms of the 6-membered ring in which the R ⁴ is present, or a substituent may be formed on the condensed ring. May have.
n indicates the number of ^R4 existing on the 6-membered ring, and indicates 0 to 4. ]

As a specific example of the halogen atom, a specific example of the halogen atom described for the substituents of L ¹ and L ² can be given for ^R4 as well.
As a specific example of the hydrocarbon group having 1 to 9 carbon atoms, among the specific examples of the hydrocarbon group having 1 to 20 carbon atoms described for the substituents of L ¹ and L ² , the example having 1 to 9 carbon atoms will be used. ^R4 can also be mentioned. Specific examples of the case where ^R4 is a hydrocarbon group having 1 to 9 carbon atoms include an alkyl having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group and a t-butyl group. Examples thereof include an alkenyl group having 1 to 4 carbon atoms such as a group, a vinyl group, a propenyl group and a butenyl group.
As specific examples of the alkoxy groups having 1 to 9 carbon atoms, among the specific examples of the alkoxy groups having 1 to 20 carbon atoms described for the substituents of L ¹ and L ² , the example having 1 to 9 carbon atoms is referred to as ^R4 . Can also be mentioned. Specific examples of the case where R ⁴ is an alkoxy group having 1 to 9 carbon atoms include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group.

As a specific example of the halogen-substituted hydrocarbon group having 1 to 9 carbon atoms, among the specific examples of the halogen-substituted hydrocarbon group having 1 to 20 carbon atoms described with respect to the substituents L ¹ and L ² , the carbon atoms 1 to 9 are used. An example of ^R4 can also be given. Specific examples of the case where ^R4 is a halogen-substituted hydrocarbon group having 1 to 9 carbon atoms include a trifluoromethyl group and a 2,2,2-trifluoroethyl group.
As a specific example of the hydrocarbon group having 3 to 9 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, the carbon number 3 containing an oxygen atom, a sulfur atom or a nitrogen atom described above for the substituents of L ¹ and L ² Among the specific examples of the hydrocarbon groups of about 20 to 20, examples having 3 to 9 carbon atoms can also be mentioned for ^R4 . Specific examples of the case where R ⁴ contains an oxygen atom include a hydrocarbon group having 5 to 8 carbon atoms and containing an oxygen atom such as a methoxybutyl group, an ethoxybutyl group, a methoxyhexyl group and an ethoxyhexyl group. Specific examples of the case where R ⁴ contains a sulfur atom include a hydrocarbon group having 5 to 8 carbon atoms including a sulfur atom such as a methylthiobutyl group, an ethylthiobutyl group, a methylthiohexyl group and an ethylthiohexyl group. Be done. Specific examples of the case where R ⁴ contains a nitrogen atom include a hydrocarbon group having 6 to 8 carbon atoms containing a nitrogen atom such as a dimethylaminobutyl group and a dimethylaminohexyl group.

As a specific example of the hydrocarbon group-substituted silyl group having 1 to 9 carbon atoms, among the specific examples of the hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms described above for the substituents L ¹ and L ² , the carbon number 1 Examples of 9 to 9 can also be given for ^R4 . Specific examples of the case where R ⁴ is a hydrocarbon group-substituted silyl group having 1 to 9 carbon atoms include a hydrocarbon group-substituted silyl group having 1 to 2 carbon atoms such as a trimethylsilyl group and a triethylsilyl group.
Specific examples of the amino group optionally substituted with a hydrocarbon group having 1 to 9 carbon atoms include an alkyl group having 1 to 4 carbon atoms such as a dimethylamino group, a diethylamino group and a dibutylamino group. Examples include class amino groups.

Specific examples of the transition metal compound in which M ¹ is a zirconium atom and X ¹ and X ² are chlorine atoms in the formula (1) include the following.

As M ¹ , a titanium atom or a hafnium atom can be used in addition to the zirconium atom, but a zirconium atom is preferable.
Among the above compounds, the cyclic structure formed by J ¹ , J ² , R ¹ and R ² is preferably a benzene-1,2-diyl group, that is, a benzene ring, and the compound number in the above table is 5. , 6, 7, 8, 9, 10, 11, 13, 14, 15, 19, 20, 21 are more preferable, and those having compound numbers 5, 6, 7, 10, 11, 14, 15 are particularly preferable. preferable.

The transition metal compound represented by the formula (1) can be produced by utilizing a general method for synthesizing a metallocene compound.
As a general procedure, an indenyl lithium salt is synthesized from indene and butyl lithium, and two equivalents of the lithium salt are reacted with α, α'-dibromo-orthoxylene to be a ligand for metallocene. Synthesize α, α'-bis (1-indenyl) -ortoxylene. After that, a lithium salt of the ligand can be further synthesized with butyl lithium and then reacted with zirconium tetrachloride to obtain metallocene.
By using a compound having various cyclopentadienyl structures instead of the above indene, a metallocene compound in which L ¹ and L ² are changed can be obtained, and a transition metal compound represented by the formula (1) is synthesized. In this case, it is possible to refer to Example 1 of JP-A-9-286812 and the synthesis example of compound 1a described in Journal of Organometallic Chemistry 535 (1997) 29-32.
In the case of synthesizing a compound in which R ¹ and R ² and J ¹ and J ² together form a cyclic structure in the formula (1), or the cyclic structure further forms a polycyclic structure, as described above. A raw material compound in which the portions corresponding to R ¹ and R ² and J ¹ and J ² of the formula (1) already form a monocyclic or polycyclic cyclic structure may be used, or during synthesis or during synthesis. A cyclic structure may be formed by reacting R ¹ and R ² to close the ring at the final stage.

2. 2. Ingredient (II)
The component (II) used in the present invention is a transition metal compound selected from the compound group represented by the following formula (2), formula (3) or formula (4).
[Compound of formula (2)]
In the present invention, a transition metal compound represented by the following formula (2) can be used as the component (II).
Equation (2):
A ³ _q L ³ L 3'M ³ X ³ X ^{3 '}

[During the ceremony,
M ³ indicates a transition metal of Group 4 of the periodic table.
L ³ and L ^{3'independently} represent ligands containing a cyclopentadienyl structure and are coordinated to M ³ . The ligand containing the cyclopentadienyl structure has a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms containing 1 to 6 silicon atoms. Substituted with a hydrocarbon group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group substituted silyl group having 1 to 20 carbon atoms. It may have been. If adjacent substituents are present on L ³ or L ^3' , they may be combined to form a ring structure.
X ³ and X ^3'contain a hydrogen atom ^, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom independently of each other. A hydrocarbon group having 3 to 20 carbon atoms or a hydrocarbon group substituted amino group having 1 to 20 carbon atoms is shown.
A ³ indicates a cross-linking group that crosslinks L ³ and L ^3' , and may or may not be present, and if present, has a cross-linking structure between L ³ and L ^3' .
q is 0 or ¹ and indicates the number of A3. ]

M ³ is a transition metal of Group 4 of the periodic table, and for example, a titanium atom (Ti), a zirconium atom (Zr) or a hafnium atom (Hf) is used as M ³ , but the point of high activation of the catalyst is Therefore, a zirconium atom is preferable.

L ³ and L ^3'contain a cyclopentadienyl structure and are ligands that coordinate to M ³ . Examples of the ligand containing a cyclopentadienyl structure include a ligand having a cyclopentadienyl skeleton, a ligand having an indenyl skeleton, and a ligand having a fluorenyl skeleton.
The ligands L ³ and L ^3'can be in the following combinations: both ligands with a substituted or unsubstituted cyclopentazinyl skeletal; both with a substituted or unsubstituted indenyl skeletal. Ligand; a ligand with a substituted or unsubstituted fluorenyl skeleton; L ³ is a ligand with a substituted or unsubstituted cyclopentadienyl skeleton, and L ^3'is a substituted or unsubstituted indenyl skeleton. Ligand with; L ³ is a ligand with a substituted or unsubstituted cyclopentadienyl skeleton and L ^3'is a ligand with a substituted or unsubstituted fluorenyl skeleton; L ³ is a substituted or unsubstituted A ligand having an indenyl skeleton and having a fluorenyl skeleton in which L ^3'is substituted or unsubstituted.
Among these combinations, L ³ and L ^3'are both ligands having a substituted or unsubstituted indenyl skeleton, and L ³ is a ligand having a substituted or unsubstituted cyclopentadienyl skeleton. A combination in which L ^3'is a ligand having a substituted or unsubstituted fluorenyl skeleton and a combination in which both are ligands having a substituted or unsubstituted fluorenyl skeleton are preferable.

The ligands L ³ and L ^3'are a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a hydrocarbon having 1 to 20 carbon atoms including 1 to 6 silicon atoms. Substituted with a group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group substituted silyl group having 1 to 20 carbon atoms. May be. Further, when adjacent substituents are present on L ³ or L ^3' , they may be bonded to form a ring structure.

As a specific example of the halogen atom, a specific example of the halogen atom described for the substituents of L ¹ and L ² can be given for L ³ and L ^3' .
As specific examples of the hydrocarbon groups having 1 to 20 carbon atoms, specific examples of the hydrocarbon groups having 1 to 20 carbon atoms described above for the substituents of L ¹ and L ² are also given for L ³ and L ^3' . be able to.
As specific examples of the alkoxy groups having 1 to 20 carbon atoms, specific examples of the alkoxy groups having 1 to 20 carbon atoms described above for the substituents of L ¹ and L ² may be given for L ³ and L ^3' . can.
As a specific example of the hydrocarbon group having 1 to 20 carbon atoms containing 1 to 6 silicon atoms, 1 to 20 carbon atoms containing 1 to 6 silicon atoms described above for the substituents of L ¹ and L ² have been described. Specific examples of the hydrocarbon group of L ³ and L ^3'can also be mentioned.

As specific examples of the halogen-substituted hydrocarbon groups having 1 to 20 carbon atoms, specific examples of the halogen-substituted hydrocarbon groups having 1 to 20 carbon atoms described above for the substituents L ¹ and L ² are L ³ and L ³ . ^' Can also be mentioned.
As a specific example of the hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, the carbon number 3 containing an oxygen atom, a sulfur atom or a nitrogen atom described above for the substituents of L ¹ and L ² Specific examples of up to ²⁰ hydrocarbon groups can also be given for L3 and L3 ^' .
Specific examples of the hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms include L3 and specific examples of the hydrocarbon group ^- substituted silyl group having ¹ to ²⁰ carbon atoms described with respect to the substituents L1 and L2. L ^3'can also be mentioned.

When both L ³ and L ^3'are substituted indenyl groups, at least one, preferably both indenyl groups, have an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms at the 2-position position. It is preferable to have a frill group which may have a substituent or a thienyl group which may have a substituent.
Further, at least one, preferably both indenyl groups having an aryl group which may have a substituent at the 4-position position are also preferably used.

X ³ and X ^3'contain a hydrogen atom ^, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom independently of each other. It is a hydrocarbon group having 3 to 20 carbon atoms or a hydrocarbon group substituted amino group having 1 to 20 carbon atoms.
As specific examples of X ³ and X ^3' , specific examples explaining X ¹ and X ² of the above formula (1) can also be given for X ³ and X ^3' .

A ³ is a cross-linking group that crosslinks L ³ and L ^3' , and may or may not be present. When q in the formula (2) is 0 (zero), A ³ does not exist and there is no cross-linking structure between L ³ and L ^3' .
The compound of the formula (2) may be either a non-crosslinked metallocene or a crosslinked metallocene, but is preferably a crosslinked metallocene.

The cross-linking group A3 may have a divalent hydrocarbon group having ¹ to 20 carbon atoms which may have a substituent, a silylene group which may have a substituent, or a substituent. It is preferably any of the gelmilene groups.
Examples of the substituent include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen substituted hydrocarbon group having 1 to 20 carbon atoms, and a hydrocarbon group having 1 to 20 carbon atoms including 1 to 6 silicon atoms. , A hydrocarbon group substituted silyl group having 1 to 20 carbon atoms, and a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom can be mentioned.
When a plurality of substituents are present on A3 ^, they may be bonded to each other to form a ring structure.

Specific examples of A3 include an alkylene group such as methylene ^, methylmethylene, dimethylmethylene and 1,2-ethylene; an arylalkylene group such as diphenylmethylene; a silylene group; a methylsilylene, a dimethylsilylene, a diethylsilylene and a di (n-). Alkylylylene group such as propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, (alkyl) (aryl) silylene group such as methyl (phenyl) silylene; arylcyrylene group such as diphenylsilylene; tetramethyldi Examples thereof include an alkyloligosilylene group such as silylene; a gelmilene group; an alkyl gelmilene group in which the silicon of the above alkylsilylene group is replaced with germanium; an (alkyl) (aryl) gelmilene group; an aryl gelmilene group and the like.
When forming a ring structure, a divalent group having a structure such as silacyclobutane, silacyclopentane, 2,5-dimethylsilacyclopentane, silacyclohexane, or silafluorene, which is a 4- to 7-membered ring, is mentioned. Can be done.
Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a gelmilene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylcilylene group and an alkylgelmilene group are particularly preferable.

Among the transition metal compounds represented by the formula (2), the transition metal compound represented by the following formula (2-1) is preferable.

[During the ceremony,
M ³ represents a titanium atom (Ti), a zirconium atom (Zr) or a hafnium atom (Hf).
X ³ and X ^3'are the same as X ³ and X ^3'in the above equation (2), respectively.
Y represents a carbon atom, a silicon atom or a germanium atom.
Each of R ¹¹ and R ²¹ independently has a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a frill group or a substituent which may have a substituent. Indicates a thienyl group which may be present. At least one of R ¹¹ and R ²¹ is either a frill group which may have a substituent or a thienyl group which may have a substituent.
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ , respectively. Independently, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a halogen substituted alkyl group having 1 to 6 carbon atoms, and a trialkyl group. An alkyl group having 1 to 6 carbon atoms having a silyl group, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, a halogen-substituted aryl group having 6 to 18 carbon atoms or a substituent. A heterocyclic group constituting a 5-membered ring or a 6-membered ring which may be possessed is shown. Adjacent groups of R ¹² to R ¹⁹ and R ²² to R ²⁹ may be bonded to each other to form a 6 to 7-membered ring, or the 6 to 7-membered ring may contain an unsaturated bond.
Each of R ³¹ and R ³² independently has a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a halogen-substituted alkyl group having 1 to 6 carbon atoms, and a trialkylsilyl group. It has an alkyl group having 1 to 6 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a halogen-substituted aryl group or a substituent having 6 to 18 carbon atoms. It shows a heterocyclic group constituting a good 5-membered ring or 6-membered ring. R ³¹ and R ³² may form a 4- to 7-membered ring together with Y, and if at least one of R ³¹ and R ³² has a cyclic structure, it is composed of R ³¹ and R ³² and Y 4 The 7-membered ring may form a fused ring that shares a part of the constituent atoms of the cyclic structure of R ³¹ and R ³² . ]

Among the transition metal compounds represented by the formula (2), the following can be mentioned as preferable ones.
(I) Bisindene type {1,1'-dimethylsilylenebis (2-methyl-4-phenylindenyl)} zirconium dichloride,
[1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2-methyl-4- (4-i-propylphenyl) indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2-methyl-4- (4-trimethylsilylphenyl) indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2-methyl-4- (3-chloro-4-t-butylphenyl) indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2-methyl-4- (3-methyl-4-t-butylphenyl) indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2-methyl-4- (2-naphthyl) indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenyl) indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2-methyl-4- (2-chloro-4-biphenyl) indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2-methyl-4- (9-phenanthril) indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2-methyl-4- (4-chloro-2-naphthyl) indenyl}] zirconium dichloride,

[1,1'-dimethylsilylenebis {2-ethyl-4- (4-chlorophenyl) indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2-n-propyl-4- (3-chloro-4-trimethylsilylphenyl) indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-t-butylphenyl) indenyl}] zirconium dichloride,
[1,1'-dimethylgelmilenebis {2-methyl-4- (2-fluoro-4-biphenyl) indenyl}] zirconium dichloride,
[1,1'-dimethylgelmilenebis {2-methyl-4- (4-t-butylphenyl) indenyl}] zirconium dichloride,
[1,1'-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) indenyl}] zirconium dichloride,

Further, as a compound in which the position of the 2-position of the indenyl group is a frill group or a thienyl group,
[1,1'-dimethylsilylenebis {2- (2-furyl) -4-phenyl-indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (2-thienyl) -4-phenyl-indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] zirconium dichloride,
[1,1'-Diphenylcilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] zirconium dichloride,
[1,1'-dimethylgelmilenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] zirconium dichloride,
[1,1'-dimethylgelmilenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-trimethylsilyl-2-furyl) -4-phenyl-indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] zirconium dichloride dichloride,
[1,1'-dimethylsilylenebis {2- (2-benzofuryl) -4-phenyl-indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (2-furfuryl) -4-phenyl-indenyl}] zirconium dichloride,

[1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) -indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl}] zirconium dichloride,

[1,1'-dimethylsilylenebis {2- (2-furyl) -4- (1-naphthyl) -indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthrill) -indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthril) -indenyl}] zirconium dichloride,

[1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-phenanthrill) -indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (9-phenanthryl) -indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-t-butyl-2-frill) -4- (2-phenanthrill) -indenyl}] zirconium dichloride,
[1,1'-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (9-phenanthryl) -indenyl}] zirconium dichloride, and the like.

(Ii) Cyclopentadienyl-fluorenyl-type diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,
Diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,
Diphenylmethylene (1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride,
Diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride,
Isopropyridene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride,
Isopropyridene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride,
Examples thereof include diphenylsilanediyl (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, dimethylsilanediyl (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, and the like.

(Iii) Bisfluorenyl type dimethylsilanediylbis (fluorenyl) zirconium dichloride,
Di (n-butyl) silanediylbis (fluorenyl) zirconium dichloride,
Diethylsilanediylbis (1-methylfluorenyl) zirconium dichloride,
(1,1-difluorenylmethane) zirconium dichloride,
(1,2-Difluolenyl) Ethanezirconium dichloride,
(1,3-Difluolenylpropane) Zirconium dichloride,
(1,2-di (1-methylfluorenyl) ethane) zirconium dichloride,
(1,2-di (2-ethylfluorenyl) ethane) zirconium dichloride,
(1,2-di (2-t-butylfluorenyl) ethane) zirconium dichloride,
(1,2-di (1-t-butylfluorenyl) ethane) zirconium dichloride,
(1,2-di (4-methylfluorenyl) ethane) zirconium dichloride,
(1,2-di (4-t-butylfluorenyl) ethane) zirconium dichloride,
(1,2-di (2,7-di-t-butyl-4-methylfluorenyl) ethane) zirconium dichloride and the like can be mentioned.

As a method for producing a transition metal compound represented by the formula (2), a compound having a cyclopentadiene structure which is the basis of the ligand structure is synthesized, and a lithium salt of the ligand is produced with butyl lithium or the like. do. Two equivalents of lithium salt are reacted with dimethyldichlorosilane to synthesize a crosslinked ligand. A crosslinked metallocene compound can be obtained by reacting this crosslinked ligand with 2 equivalents of butyl lithium to form a dilithium salt and reacting this with zirconium tetrachloride. Various metallocene compounds can be obtained by using cyclopentadiene, indene, and fluorene having a substituent bonded to the compound having a cyclopentadiene structure used first. Further, by reacting the lithium salt of the ligand with one equivalent of dimethyldichlorosilane and then reacting with the lithium salt of another ligand, a ligand having a different structure cross-linked is obtained. You can also do it.

[Compound of formula (3)]
In the present invention, a transition metal compound represented by the following formula (3) can be used as the component (II).
Equation (3):
A ⁴ L ⁴ M ⁴ X ⁴ X ^4'

[During the ceremony,
M ⁴ indicates a transition metal of Group 4 of the periodic table.
L ⁴ represents a ligand containing a cyclopentadienyl structure and is coordinated to M ⁴ . The ligand containing the cyclopentadienyl structure has a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms containing 1 to 6 silicon atoms. Substituted with a hydrocarbon group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group substituted silyl group having 1 to 20 carbon atoms. It may have been.
^X4 and ^{X4'independently} form a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom, which are bonded to the metal ^M4 , respectively. A hydrocarbon group having 3 to 20 carbon atoms or a hydrocarbon group substituted amino group having 1 to 20 carbon atoms is shown.
A ⁴ represents an organic group having a hetero atom bonded to L ⁴ , and is bonded to M ⁴ via the hetero atom. ]

M ⁴ is a transition element of Group 4 of the periodic table. As M ⁴ , for example, a titanium atom (Ti), a zirconium atom (Zr) or a hafnium atom (Hf) is used, and a titanium atom is preferably used.
L ⁴ contains a cyclopentadienyl structure and is a ligand coordinated to M ⁴ . Examples of the ligand containing a cyclopentadienyl structure include a ligand having a cyclopentadienyl skeleton, a ligand having an indenyl skeleton, and a ligand having a fluorenyl skeleton.
The ligand L ⁴ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms including 1 to 6 silicon atoms, and a hydrocarbon group having 1 to 20 carbon atoms. It may be substituted with a halogen-substituted hydrocarbon group of 1 to 20, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms.
As a specific example of the above-mentioned substituent of the ligand L ⁴ , a specific example explaining the ligand L ³ of the transition metal compound represented by the above formula (2) can also be given for L ⁴ .

X ⁴ and X ^4'contain a hydrogen atom, a halogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom independently of each other. It is a hydrocarbon group having 3 to 20 carbon atoms or a hydrocarbon group substituted amino group having 1 to 20 carbon atoms.
As specific examples of X ⁴ and X ^4' , specific examples explaining X ¹ and X ² of the above formula (1) can also be given for X ⁴ and X ^4' .

A ⁴ is an organic group having a hetero atom bonded to L ⁴ , and is bonded to M ⁴ via the hetero atom. At this time, A ⁴ is divided into an organic group Q bonded to L ⁴ and a portion Z having a hetero atom, and can be described as QZ.
The Q of the QZ structure includes a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. Examples thereof include a gelmillene group which may have a hydrocarbon group. Specific examples include a dimethylsilylene group, a diethylsilylene group, a di-i-propylsilylene group, a diphenylcilylene group, a methylphenylcilylene group, a methyl-i-propylsilylene group, a dimethylgermylene group, a diethylgermylene group, and a di-. i-propyl gelmilene group, diphenyl gelmilene group, methylphenyl gelmilene group, methyl-i-propyl gelmilene group, dimethylmethylene group, ethylene group, 1,2-dimethylethylene group, 1-phenylethylene group, 1, Examples thereof include 2-diphenylethylene group, silacyclobutane group, silacyclopentane group, 2,5-dimethylsilacyclopentane group, silacyclohexane group, silafluorene group and phenylene group.
Of these, dimethylsilylene group, di-i-propylsilylene group, diphenylcilylene group, silacyclobutane group, silacyclopentane group, silacyclohexane group and phenylene group are preferable, and dimethylsilylene group and diphenylcilylene are particularly preferable. The group is a silacyclohexane group.
Examples of Z in the QZ structure include an amide group, a phosphide group, an oxygen atom, a sulfur atom, a phenyleneoxy group or an alkylidene group, preferably an amide group, a phenyleneoxy group and an oxygen atom, and the most preferable is an amide. It is a group.

As a method for producing the transition metal compound represented by the formula (3), a metal salt of a compound having a cyclopentadiene structure is prepared, and dichlorodialkylsilane is reacted with the metal salt to make the compound having a cyclopentadiene structure dialkylchlorosilane. Generates a compound bound to. Next, when amines are reacted, they are converted to amino (dialkyl) silane groups, which are converted to lithium salts by the action of butyllithium, and then reacted with titanium tetrachloride to form a Cp compound-SiR _2- (NR). ) Coordinates to form a complex.
At this time, by changing the types of the cyclopentadiene compound and the amine compound as raw materials, various transition metal compounds of the formula (3) can be produced.

[Compound of formula (4)]
In the present invention, a transition metal compound represented by the following formula (4) can be used as the component (II).
Equation (4):
L ⁵ _m M ⁵ X ⁵ _p

[During the ceremony,
M ⁵ indicates a transition metal of Group 3 to 11 of the Periodic Table.
The m ^L5s each independently represent a hydrocarbon group substituted with a substituent having an atom selected from two or more oxygen, nitrogen, phosphorus, and sulfur atoms, and at least two of the oxygen. , Nitrogen, phosphorus, and an atom selected from sulfur atoms are bonded to ^M5 .
Each of the p X ^5s independently has a hydrogen atom, a halogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon containing an oxygen atom or a nitrogen atom. The number 3 to 20 hydrocarbon groups or neutral Lewis bases are shown.
m represents the number of L5 and is ¹ or 2.
p indicates the number of X, which is the number selected so that the transition metal compound of the formula (4) is electrically neutral. ]

M ⁵ is a transition element of Groups 3 to 11 of the Periodic Table. Examples of M ⁵ include a scandium atom, a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a niobium atom, a tantalum atom, a cobalt atom, a rhodium atom, an yttrium atom, a chromium atom, a molybdenum atom, a tungsten atom, a manganese atom, and a renium. Atoms, iron atoms, ruthenium atoms, osnium atoms, and iridium atoms are used, but are preferably scandium atoms, titanium atoms, zirconium atoms, hafnium atoms, vanadium atoms, niobium atoms, tantalum atoms, cobalt atoms, rhodium atoms, and the like. More preferably, it is a titanium atom, a zirconium atom, a hafnium atom, a cobalt atom, a rhodium atom, a vanadium atom, a niobium atom, a tantalum atom and the like, and particularly preferably a titanium atom, a zirconium atom and a hafnium atom.

Specific examples of L ⁵ include groups represented by the following formulas (L5-1), formula (L5-2), formula (L5-3), formula (L5-4), and formula (L5-5). .. These will be described later as part of specific examples of the transition metal compound represented by the formula (4).
As a specific example of X ⁵ , a specific example explaining X ¹ and X ² of the above formula (1) can also be given for X ⁵ .

Specific examples of the transition metal compound represented by the formula (4) include the following formulas (4-1), formulas (4-2), formulas (4-3), formulas (4-4), and formulas (4). The groups shown in -5) can be mentioned.
Of these, the compounds listed in the formulas (4-2) and (4-4) are preferable because the difference in molecular weight when combined with the component (I) is appropriate.

[Transition metal compound represented by the formula (4-1)]
The transition metal compound represented by the formula (4-1) has a substituent represented by the formula ( ^L5-1 ) as L5 of the formula (4).

[In the formula (4-1) and the formula (L5-1),
M ⁵ indicates a transition metal atom of Group 3 to 6 of the Periodic Table.
Each of ^X5 has a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom or a nitrogen atom. Is shown.
p is the valence of ^M5-2 .
Each of R ⁵¹ and R ⁵² is independently selected from a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an organic silyl group or a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom and a silicon atom. Indicates a substituent having the element of.
m is an integer of 0 to 2, and n is an integer of 1 to 5.
A indicates an atom of Group 13 to 16 of the periodic table.
When n is 2 or more, the plurality of A's may be the same or different from each other.
E represents a substituent having at least one element selected from a carbon atom, a hydrogen atom, an oxygen atom, a halogen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a boron atom and a silicon atom.
When m is 2 or more, the plurality of Es may be the same or different from each other, or two or more groups represented by E may be connected to each other to form a ring. ]

R ⁵¹ and R ⁵² are substituteds having at least one element selected from a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an organic silyl group or a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom and a silicon atom. It is the basis.
Examples of the hydrocarbon group include a linear or branched alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group and a t-butyl group; and an aryl group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group. A substituted aryl group in which 1 to 5 substituents such as an alkyl group having 1 to 20 carbon atoms are substituted on these aryl groups; a cycloalkyl group such as a cyclopentyl group and a norbornyl group; a vinyl group, a propenyl group and a cyclohexenyl group. Alkenyl groups such as benzyl group, phenylethyl group, arylalkyl group such as phenylpropyl group and the like.
Examples of the halogenated hydrocarbon group include a group in which the hydrocarbon group is substituted with a halogen.
Examples of the organic silyl group include a methylsilyl group, a trimethylsilyl group, an ethylsilyl group, a triphenylsilyl group and the like.
Examples of the hydrocarbon group substituted with a substituent containing at least one element selected from a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom and a silicon atom include -COOCH ₃ , -N (in the above-mentioned hydrocarbon group). CH ₃ ) C (O) CH ₃ , -OC (O) CH ₃ , -CN, -N (C ₂ H ₅ ) ₂ , -N (CH ₃ ) S (O ₂ ) CH ₃ , -P (C ₆ ) H ₅ ) Examples thereof include groups substituted with ₂ and the like.

A is an atom of Group 13 to 16 of the periodic table, and examples thereof include a boron atom, a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a sulfur atom, a germanium atom, a selenium atom, and a tin atom. ..
E is a substituent having at least one element selected from a carbon atom, a hydrogen atom, an oxygen atom, a halogen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a boron atom and a silicon atom.
Examples of the bonding group that binds the two nitrogen atoms represented by-((E m) A) n- include the following groups: -CH _2- , -C (Me) ₂ . -, -C (Ph) _2- , -Si (Me) _2- , -Si (Ph) _2- , -Si (Me) (Ph)-, -CH ₂ CH ₂ CH _2- , -CH ₂ C ( nPr) ₂ CH _2- , -CH ₂ C (cHex) ₂ CH _2-

The transition metal compound represented by the above formula (4-1) is similar to the compound (I-1) of JP-A No. 10-330412, and the publication can be referred to.

[Transition metal compound represented by the formula (4-2)]
The transition metal compound represented by the formula (4-2) has a substituent represented by the formula ( ^L5-2 ) as L5 of the formula (4).

[In the formula (4-2) and the formula (L5-2),
M ⁵ indicates a transition metal atom of Group 3 to 11 of the Periodic Table.
m represents an integer of 1 to 2.
R ⁵³ to R ⁵⁸ are independently hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, and silicon. It indicates a containing group, a germanium-containing group, or a tin-containing group, and two or more of them may be linked to each other to form a ring.
n represents a number satisfying the valence of ^M5 .
Each of ^X5 independently contains a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom or a nitrogen atom. show. ]

R ⁵³ to R ⁵⁸ contain a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, and a germanium-containing group. A group or a tin-containing group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the hydrocarbon group include a linear or branched alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group and a t-butyl group; and a vinyl group, an allyl group, an isopropenyl group and the like having 2 carbon atoms. Linear or branched alkenyl group of ~ 30; Linear or branched alkynyl group having 2 to 30 carbon atoms such as propargyl group; Cyclic saturated hydrocarbon having 3 to 30 carbon atoms such as cyclohexyl group and adamantyl group Group; Cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl group, indenyl group and fluorenyl group; Aromatic group having 6 to 30 carbon atoms such as phenyl group, benzyl group, naphthyl group and biphenyl group. Examples thereof include alkyl-substituted aromatic groups such as trill group, t-butylphenyl group and di-t-butylphenyl group.
The above-mentioned hydrocarbon group is a halogen atom such as a fluorine atom; another hydrocarbon group; a heterocyclic compound residue described later, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, and a silicon-containing group. It may be substituted with a group, a germanium-containing group, or a tin-containing group.
Examples of the heterocyclic compound residue include a nitrogen-containing compound such as a pyrrole group and a pyridine group, an oxygen-containing compound such as a furan group and a pyran group, a residue such as a sulfur-containing compound such as a thiophene group, and a heterocycle thereof. Examples of the compound residue include a group having 1 to 30 carbon atoms and a group further substituted with a substituent such as an alkoxy group.

Examples of the oxygen-containing group include an alcohol group, an aryloxy group, an ester group, an ether group, an acyl group and the like.
Examples of the nitrogen-containing group include an amino group, an imino group, an amide group, a hydrazino group, a nitro group, a cyano group and the like.
Examples of the boron-containing group include a bolangyyl group, a bolantriyl group, and a diboranyl group.
Examples of the sulfur-containing group include a mercapto group, a thioester group, an arylthio group, a thioacyl group, a thioether group, a thiosian acid ester group, a sulfo group, a sulfonyl group and the like.
Examples of the phosphorus-containing group include a phosphido group, a phosphoryl group, a thiophosphoryl group, a phosphat group and the like.
Examples of the silicon-containing group include a silyl group; a syroxy group; a methylsilyl group, a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a dimethylphenylsilyl group and the like, and a hydrocarbon substituted silyl group such as a trimethylsiloxy group. The group etc. can be mentioned.
Examples of the germanium-containing group and the tin-containing group include those in which the silicon of the silicon-containing group is replaced with germanium and tin.

The transition metal compound represented by the above formula (4-2) is similar to the transition metal compound (B) represented by the general formula (I) of JP-A-2000-63415, and the relevant publication is referred to. Can be.

[Transition metal compound represented by the formula (4-3)]
The transition metal compound represented by the formula (4-3) has a substituent represented by the formula ( ^L5-3 ) as L5 of the formula (4).

[In the formula (4-3) and the formula (L5-3),
M ⁵ indicates a transition metal atom of Group 8 to 11 of the Periodic Table.
R ⁶¹ to R ⁶⁴ are independently hydrogen atom, halogen atom, halogenated hydrocarbon group, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group. , Phosphorus-containing group, silicon-containing group, germanium-containing group, tin-containing group and the like.
R ⁶⁵ and R ⁶⁶ each independently contain a halogen atom, a halogenated hydrocarbon group, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, and a phosphorus-containing group. A group, a silicon-containing group, a germanium-containing group, a tin-containing group, and the like are shown. Further, R ⁶¹ and R ⁶⁵ may be connected to each other to form a ring, R ⁶² and R ⁶⁶ may be connected to each other to form a ring, and R ⁶¹ and R ⁶³ may be connected to each other to form a ring. A ring may be formed, R ⁶² and R ⁶⁴ may be connected to each other to form a ring, and R ⁶³ and R ⁶⁴ may be connected to each other to form a ring.
n represents the valence of ^M5 .
Reference numeral ^X5 indicates a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom or a nitrogen atom.
When n is 2 or more, the plurality of groups represented by X ⁵ may be the same or different from each other.
Y indicates an atom of Group 15 or Group 16 of the periodic table. ]

Halogen atoms of R ⁶¹ to R ⁶⁴ , R ⁶⁵ and R ⁶⁶ , halogenated hydrocarbon groups, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing As specific examples of the group, the silicon-containing group, the germanium-containing group or the tin-containing group, the specific examples described for R ⁵³ to R ⁵⁸ of the above formula (4-2) are described as R ⁶¹ to R of the formula (4-3). ⁶⁴ , R ⁶⁵ and R ⁶⁶ can also be mentioned.

The transition metal compound represented by the above formula (4-3) is similar to the transition metal imine compound represented by the general formula (I) of JP-A-2000-191719, and the relevant publication is referred to. Can be.

[Transition metal compound represented by the formula (4-4)]
The transition metal compound represented by the formula (4-4) has a substituent represented by the formula ( ^L5-4 ) as L5 of the formula (4).

[In the formula (4-4) and the formula (L5-4),
R ⁶⁷ and R ⁶⁸ independently represent alkyl, aryl, heterocyclic groups and hydrogen atoms, respectively.
R ⁶⁹ and R ⁷⁰ are independently halogen atoms, hydrogen atoms, alkyls having 1 to 20 carbon atoms, aryls, alkenyls, alkylaryls, arylalkyls, hydrocarboxy groups, amides, phosphides, sulfides, silylalkyls, and diketonates. And carboxylate.
Each X ⁵ independently has a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydrocarbon having 3 to 20 carbon atoms including an oxygen atom or a nitrogen atom. Shows the group. ]

The transition metal compound represented by the above formula (4-4) is similar to the second metal compound represented by the general formula described in paragraph 0027 of Japanese Patent Application Laid-Open No. 2003-515628. It can be used as a reference. Further, the compound 1 described in paragraph 0030 of the relevant publication and the compound 2 described in paragraph 0031 can be used as the transition metal compound of the formula (4-4) in the present invention.

[Transition metal compound represented by the formula (4-5)]
The transition metal compound represented by the formula (4-5) has a substituent represented by the formula ( ^L5-5 ) as L5 of the formula (4).

[In the formula (4-5) and the formula (L5-5),
n is 1, 2 or 3.
M ⁵ represents a zirconium atom or a hafnium atom.
R ⁷¹ to R ⁷⁸ each have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 3 to 20 carbon atoms including an oxygen atom or a nitrogen atom. A hydrocarbon group having 1 to 20 carbon atoms substituted with a hydrocarbon group or a halogen is shown.
Each of ^X5 has a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom or a nitrogen atom. X ^5L indicates a neutral Lewis base. When there are a plurality of X ^5Ls , the plurality of X ^5Ls may be the same or different.
l is 0, 1, or 2. ]

R ⁷¹ to R ⁷⁸ are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom or a nitrogen atom, or a halogen. It is a hydrocarbon group having 1 to 20 carbon atoms substituted with.
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 such as a methyl group, an ethyl group and a t-butyl group; a linear group such as a vinyl group, an allyl group and an isopropenyl group. Or a branched alkenyl group; a linear or branched alkynyl group such as a propargyl group; a cyclic saturated hydrocarbon group such as a cyclohexyl group or an adamantyl group; a cyclic unsaturated group such as a cyclopentadienyl group, an indenyl group or a fluorenyl group. Hydrocarbon groups; aromatic groups such as phenyl group, benzyl group, naphthyl group and biphenyl group; alkyl substituted aromatic groups such as tolyl group, t-butylphenyl group and di-t-butylphenyl group can be mentioned.

Examples of the hydrocarbon group having 1 to 20 carbon atoms including an oxygen atom include a hydrocarbon group having an oxygen-containing group such as an alcoholic group, an aryloxy group, an ester group, an ether group and an acyl group.
Examples of the hydrocarbon group having 1 to 20 carbon atoms including a nitrogen atom include a hydrocarbon group having a nitrogen-containing group such as an amino group, an imino group, an amide group, a hydrazino group, a nitro group and a cyano group.
Examples of the halogen-substituted hydrocarbon group having 1 to 20 carbon atoms include a trifluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group and a pentafluorophenyl group.

The transition metal compound represented by the above formula (4-5) is similar to the component (A1) represented by the general formula (1-1) described in JP2013-53308. The publication can be referred to.

II. Catalyst for olefin polymerization The above component (I) and the above component (II) are each catalytically active components for olefin polymerization, but the combination thereof has a sufficiently wide molecular weight distribution and a wide distribution on the high molecular weight side. Moreover, it acts as a catalytically active component of a catalyst for olefin polymerization capable of producing an olefin-based polymer containing a sufficient amount of branched chains in the high-molecular-weight side region of the molecular weight distribution.
The above component (I) and the above component (II) can be combined with a co-catalyst or a carrier to prepare a catalyst for olefin polymerization.
In the present invention, for example, an olefin polymerization catalyst containing the following components (I), component (II), component (III) and component (IV) as essential components can be used. Two or more kinds of each component may be used.
Component (I): Transition metal compound represented by the above formula (1) Component (II): Transition metal compound selected from the compound group represented by the above formula (2), (3) or (4) Component (III) ): A compound that reacts with the transition metal compound of the component (I) and the component (II) to form a cationic compound. Component (IV): Fine particle carrier

The component (I) and the component (II) are as described above. The component (III) and the component (IV) will be described below.
1. 1. Ingredient (III)
The component (III), that is, the compound that reacts with the transition metal compound of the component (I) and the component (II) to form a cationic compound is a co-catalyst. As the component (III), for example, an organoaluminum oxy compound, a borane compound, a borate compound, a layered silicate described later, or the like can be used. Of these, borane and borate compounds have difficulty in immobilizing on a fine particle carrier, and organoaluminum oxy compounds are preferably used.

(1) Organic Aluminum Oxy Compound The organic aluminum oxy compound is a compound having an Al—O—Al bond in the molecule, and the number of Al—O—Al bonds is usually 1 to 100, preferably 1 to 50. It is in the range.
Typically, an organoaluminum oxy compound containing a chain structure of-(O-Al) -units as represented by the following formula (5-1) or formula (5-2) is used.

[In each of the above formulas, R ⁴¹ is independently a hydrogen atom or a hydrocarbon group, preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, an alkenyl group, or an aryl group. It is a hydrocarbon group such as an aralkyl group, and at least a part of R ⁴¹ is a hydrocarbon group. p represents an integer of 0 to 40, preferably 2 to 30. ]

Such an organoaluminum oxy compound is usually obtained by reacting an organoaluminum compound with water.
The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon (solvent). As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used, but aliphatic hydrocarbons or It is preferable to use aromatic hydrocarbons.

As the organoaluminum compound as a raw material, a compound represented by the following formula (6) can be used, but trialkylaluminum is preferably used.
R ⁴¹ _t AlX ⁶ _3-t formula (6)
[In the formula (6), R ⁴¹ is the same as the above formulas (5-1) and (5-2), X ⁶ represents a hydrogen atom or a halogen atom, and t is 1 ≦ t ≦ 3. Indicates an integer. ]

The alkyl group of trialkylaluminum may be any of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and the like, but a methyl group. Is particularly preferable. The above-mentioned organoaluminum compounds can also be used by mixing two or more kinds.

The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is 0.25 / 1 to 1.2.
1/1, particularly preferably 0.5 / 1/1 to 1/1, and the reaction temperature is usually in the range of −70 to 100 ° C., preferably −20 to 20 ° C. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours.
As the water required for the reaction, not only water but also water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate and the like, and components capable of producing water in the reaction system can be used.

An organoaluminum oxy compound using trimethylaluminum as a raw material organoaluminum compound is called methylaluminoxane (MAO) and is particularly preferably used. MAO can also be used as component (III) in the form of unreacted trimethylaluminum. This unreacted trimethylaluminum is present in an amount of 1 to 30 mol% with respect to the total aluminum atom of trimethylaluminum and methylaluminoxane. It is difficult to use due to the high risk of. A MAO solution containing 10 to 15 mol% of trimethylaluminum is preferable. In addition, if the concentration of MAO is too high, the risk of handling increases, MAO precipitates during storage, making it difficult to use, and if it is thin, safety and difficulty in precipitation increase, but the containers and equipment handled are It becomes large and becomes an economic disadvantage. The concentration of MAO is preferably 10 to 20% by mass. Further, since the MAO solution tends to precipitate in the temperature, it is preferable to store it at a low temperature below −10 ° C.
Of course, as the organoaluminum oxy compound, two or more of the above-mentioned organoaluminum oxy compounds can be used in combination, and the organoaluminum oxy compound can be used as a solution or a solution obtained by dispersing the organoaluminum oxy compound in the above-mentioned inert hydrocarbon solvent. You may use the one that has been used.

(2) Borane compounds Examples of borane compounds include the following compounds: triphenylborane, tri (o-tolyl) borane, tri (p-tolyl) borane, tri (m-tolyl) borane, tri (o). -Fluorophenyl) borane, tris (p-fluorophenyl) borane, tris (m-fluorophenyl) borane, tris (2,5-difluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-) Trifluoromethylphenyl) borane, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (Perfluorobiphenyl) borane, tris (perfluoroanthril) borane, tris (perfluorobinaphthyl) borane.

Among these, the following compounds are preferred: tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl). Borane, tris (perfluorobiphenyl) borane, tris (perfluoroanthryl) borane, tris (perfluorobinaphthyl) borane are more preferred.
Among these, the following compounds are further preferred: tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluorobiphenyl) borane.

(3) Borate compound As a first example of a borate compound, for example, a compound represented by the following formula (7) can be mentioned.
[L ⁶ -H] ⁺ [BR ⁴² R ⁴³ X ⁷ X ^7' ] ^- Equation (7)

In formula (7), L ⁶ is a neutral Lewis base, H is a hydrogen atom, and [L ⁶ -H] is a Bronsted acid such as ammonium, anilinium, and phosphonium.
Examples of the ammonium include trialkyl-substituted ammonium such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium and tri (n-butyl) ammonium, and dialkylammonium such as di (n-propyl) ammonium and dicyclohexylammonium.
Examples of the anilinium include N, N-dialkylaniliniums such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium.
Further, examples of phosphonium include triarylphosphonium such as triphenylphosphine, tributylphosphonium, tri (methylphenyl) phosphonium, and tri (dimethylphenyl) phosphonium, and trialkylphosphonium.

Further, in the formula (7), R ⁴² and R ⁴³ are the same or different aromatic or substituted aromatic hydrocarbon groups having 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, and are linked to each other by a bridging group. As the substituent of the substituted aromatic hydrocarbon group, an alkyl group typified by a methyl group, an ethyl group, a propyl group, an isopropyl group and the like, and a halogen such as fluorine, chlorine, bromine and iodine are preferable.
Further, X ⁷ and X ^{7'independently} have a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and one or more hydrogen atoms having 1 to 20 carbon atoms substituted with the halogen atom. It is a substituted hydrocarbon group.

Specific examples of the compound represented by the above general formula (7) include the following compounds: tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) bolate. , Tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoronaphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) bolate, Dimethylanilinium tetra (2,6-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylaniliniumtetra (2,6-difluorophenyl) borate, dimethylaniliniumtetra (Perfluoronaphthyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5-ditrifluoromethylphenyl) borate, Triphenylphosphonium tetra (2,6-difluorophenyl) borate, triphenylphosphonium tetra (perfluoronaphthyl) borate, trimethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium tetra (pentafluorophenyl) borate, Triethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium tetra (perfluoronaphthyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (2,6-ditrifluoromethylphenyl) Borate, Tripropylammoniumtetra (Perfluoronaphthyl) Borate, Di (1-propyl) Ammonium Tetra (Pentafluorophenyl) Borate, Dicyclohexylammoniumtetraphenylborate.

Among these, the following compounds are preferred: tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, Tributylammonium tetra (perfluoronaphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) ) Bolate, dimethylanilinium tetra (perfluoronaphthyl) borate.

As a second example of the borate compound, for example, a compound represented by the following formula (8) can be mentioned.
Equation (8):
[L ⁷ ] ⁺ [BR ⁴² R ⁴³ X 7'X ^{7 '} ] ^-

In formula ( ⁸ ), L7 is a carbocation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, t-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium. Examples include cations and protons. Further, R ⁴² , R ⁴³ , X ⁷ and X ^7'are the same as the definitions in the above equation (7).

Specific examples of the compound represented by the above formula (8) include the following compounds: trityltetraphenylborate, trityltetra (o-tolyl) borate, trityltetra (p-tolyl) borate, trityltetra. (M-tril) borate, trityltetra (o-fluorophenyl) borate, trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityl Tetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropinium tetraphenylborate , Tropinium tetra (o-tolyl) borate, tropinium tetra (p-tolyl) borate, tropinium tetra (m-tolyl) borate, tropinium tetra (o-fluorophenyl) borate, tropinium tetra (p-fluorophenyl) ) Borate, Tropinium Tetra (m-Fluorophenyl) Borate, Tropinium Tetra (3,5-Difluorophenyl) Borate, Tropinium Tetra (Pentafluorophenyl) Borate, Tropinium Tetra (2,6-Ditrifluoromethylphenyl) Borate, Tropinium Tetra (3,5-Ditrifluoromethylphenyl) Borate, Tropinium Tetra (Perfluoronaphthyl) Borate, NaBPh ₄ , NaB (o-CH ₃ -Ph) ₄ , NaB (p-CH ₃ -Ph) ₄ , NaB (m-CH ₃ -Ph) ₄ , NaB (o-F-Ph) ₄ , NaB (p-F-Ph) ₄ , NaB (m-F-Ph) ₄ , NaB (3,5-F) ₂ -Ph) ₄ , NaB (C ₆ F ₅ ) ₄ , NaB (2,6- (CF ₃ ) ₂ -Ph) ₄ , NaB (3,5- (CF ₃ ) ₂ -Ph) ₄ , NaB (C) ₁₀ F ₇ ) ₄ , HBPh ₄ · (Et ₂ O) ₂ , HB (3,5-F ₂ -Ph) ₄ · (Et ₂ O) ₂ , HB (C ₆ F ₅ ) ₄ · (Et ₂ O) ₂ , HB (2,6- (CF ₃ ) ₂ -Ph) ₄ , (Et ₂ O) ₂ , HB (3,5- (CF ₃ ) ₂ -Ph) ₄ , (Et ₂ O) ₂ , H B (C ₁₀ H ₇ ) _4. (Et ₂ O) ₂ .

Among these, the following compounds are preferred: trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra ( Perfluoronaphthyl) borate, tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5-ditrifluoromethylphenyl) borate, tropinium tetra ( Perfluoronaphthyl) borate, NaB (C ₆ F ₅ ) ₄ , NaB (2,6- (CF ₃ ) ₂ -Ph) ₄ , NaB (3,5- (CF ₃ ) ₂ -Ph) ₄ , NaB (C) ₁₀ F ₇ ) ₄ , HB (C ₆ F ₅ ) ₄ , (Et ₂ O) ₂ , HB (2,6- (CF ₃ ) ₂ -Ph) ₄ , (Et ₂ O) ₂ , HB (3, 5) -(CF ₃ ) ₂ -Ph) _4. (Et ₂ O) ₂ , HB (C ₁₀ H ₇ ) _4. (Et ₂ O) ₂ .

Among these, the following compounds are further preferred: trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, tropiniumtetra (pentafluorophenyl) borate, tropiniumtetra (2,). 6-Ditrifluoromethylphenyl) Borate, NaB (C ₆ F ₅ ) ₄ , NaB (2,6- (CF ₃ ) ₂ -Ph) ₄ , HB (C ₆ F ₅ ) ₄ , (Et ₂ O) ₂ , HB (2,6- (CF ₃ ) ₂ -Ph) ₄ , (Et ₂ O) ₂ , HB (3,5- (CF ₃ ) ₂ -Ph) ₄ , (Et ₂ O) ₂ , HB (C ₁₀ ) H ₇ ) _4. (Et ₂ O) ₂ .

As the component (III), a mixture of the above-mentioned organoaluminum oxy compound and the above-mentioned borane compound or borate compound can also be used. Further, the above-mentioned borane compound and borate compound can be used by mixing two or more kinds.

2. 2. Ingredient (IV)
The component (IV), that is, the fine particle carrier, includes an inorganic carrier, a particulate polymer carrier, or a mixture thereof. As the inorganic carrier, a metal, a metal oxide, a metal chloride, a metal carbonate, a carbonaceous substance, or a mixture thereof can be used.
Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel and the like.

Examples of the metal oxide include single oxides or composite oxides of the elements of Groups 1 to 14 of the Periodic Table, and examples thereof include SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , and TiO ₂ . ZrO ₂ , Fe ₂ O ₃ , Al ₂ O ₃ · MgO, Al ₂ O ₃ · CaO, Al ₂ O ₃ · SiO ₂ , Al ₂ O ₃ · MgO · CaO, Al ₂ O ₃ · MgO · SiO ₂ , Al Various natural or synthetic single oxides or composite oxides such as ₂ O ₃ · CuO, Al ₂ O ₃ · Fe ₂ O ₃ , Al ₂ O ₃ · NiO, SiO ₂ · MgO can be exemplified. Here, the above formula represents only the composition, not the molecular formula, and the structure and component ratio of the composite oxide used in the present invention are not particularly limited. Further, the metal oxide used in the present invention may absorb a small amount of water and may contain a small amount of impurities.

As the metal chloride, for example, chlorides of alkali metals and alkaline earth metals are preferable, and specifically, MgCl ₂ and CaCl ₂ are particularly suitable. The metal carbonate is preferably a carbonate of an alkali metal or an alkaline earth metal, and specific examples thereof include magnesium carbonate, calcium carbonate and barium carbonate.
Examples of carbonaceous materials include carbon black and activated carbon.
All of the above inorganic carriers can be preferably used in the present invention, but it is preferable to use metal oxides, silica, and alumina, and it is more preferable to use silica. As the silica, it is preferable to use small particle size silica having an average particle size of about 10 μm to 150 μm. Here, the average particle size is a measurement method using laser diffraction, which is generally used, and is a value indicated as a median diameter from the data expressed by the volume standard.

These inorganic carriers are usually calcined at 200 ° C. to 800 ° C., preferably 400 ° C. to 600 ° C. in air or in an inert gas such as nitrogen or argon to reduce the amount of surface hydroxyl groups to 0.8 mmol / g to 1. It is preferable to adjust to 5.5 mmol / g before use. The properties of these inorganic carriers are not particularly limited, but usually, the average particle size is 5 μm to 200 μm, preferably 10 μm to 150 μm, the average pore diameter is 20 Å to 1000 Å, preferably 50 Å to 500 Å, and the specific surface area is 150 m ² /. g-1000m ² / g, preferably 200m ² / g-700m ² / g, pore volume 0.3cm ³ / g-2.5cm ³ / g, preferably 0.5cm ³ / g-2.0cm ³ It is preferable to use an inorganic carrier having / g and an apparent specific surface area of 0.20 g / cm ³ to 0.50 g / cm ³ , preferably 0.25 g / cm ³ to 0.45 g / cm ³ .

Of course, the above-mentioned inorganic carriers can be used as they are, but as a preliminary treatment, these carriers can be used as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum, etc. It can be used after contacting with an organic aluminum compound such as diisobutylaluminum hydride or an organic aluminum oxy compound containing an Al—O—Al bond.

III. Preparation of Catalyst for Olefin Polymerization An olefin polymerization catalyst containing components (I) and (II) as catalytically active components includes components (I) and (II), and if necessary, components (III) and (IV). ) And other co-catalysts and carriers can be mixed.
When preparing the olefin polymerization catalyst containing the component (I) and the component (II), the method for contacting the component (I) and the component (II) with the co-catalyst or the carrier is not particularly limited. For example, when the component (I) and the component (II) are brought into contact with the above component (III) and the component (IV), the following method can be arbitrarily adopted.
Method (1):
Component (I) and component (II) are first contacted with component (III) and then with component (IV). More specifically, after contacting component (I) and component (II) with one component (III), or contacting component (I) and component (II) with separately separated component (III). After that, the obtained contact-treated product is brought into contact with the component (IV).
When the component (I) and the component (II) are brought into contact with one component (III), a mixture of the component (I) and the component (II) may be brought into contact with the component (III) or with the component (I). Ingredient (II) may be brought into contact with Ingredient (III) simultaneously or sequentially.
When the component (I) and the component (II) are brought into contact with the separately separated component (III), the contact-treated product of the component (I) and the contact-treated product of the component (II) are combined with one component (IV). The contact-treated product of the component (I) and the contact-treated product of the component (II) may be brought into contact with each other, and then the two contact-treated products obtained after contacting the contact-treated product of the component (I) with the separately separated component (III) are used. It may be mixed.

Method (2):
Component (I) and component (II) are first contacted with component (IV) and then with component (III). More specifically, after contacting component (I) and component (II) with one component (IV), or contacting component (I) and component (II) with separately separated component (IV). After that, the obtained contact-treated product is brought into contact with the component (III).
When the component (I) and the component (II) are brought into contact with one component (IV), a mixture of the component (I) and the component (II) may be brought into contact with the component (IV) or with the component (I). Ingredient (II) may be brought into contact with Ingredient (IV) simultaneously or sequentially.
When the component (I) and the component (II) are brought into contact with the separately separated component (IV), the contact-treated product of the component (I) and the contact-treated product of the component (II) are combined with one component (III). The contact-treated product of the component (I) and the contact-treated product of the component (II) may be brought into contact with each other, and then the two contact-treated products obtained after contacting the contact-treated product of the component (I) with the separately separated component (III) are used. It may be mixed.

Method (3):
The component (III) and the component (IV) are first contacted to obtain a contact-treated product, and then the component (I) and the component (II) are brought into contact with the contact-treated product. More specifically, the component (III) and the component (IV) are brought into contact with each other to obtain a contact-treated product, and then the component (I) and the component (II) are brought into contact with one contact-treated product, or the component (I) is contacted. ) And component (II) are each contacted with a separately separated contact-treated product, and the obtained two contact-treated products are mixed.
When the component (I) and the component (II) are brought into contact with one contact-treated product, a mixture of the component (I) and the component (II) may be brought into contact with the contact-treated product, or the component (I) and the component (I) and the component (II) may be brought into contact with the contact-treated product. II) may be brought into contact with the contacted material simultaneously or sequentially.

Among these contact methods, the method (1) in which the component (I) and the component (II) are first contacted with the component (III), and the component (I) and the component (II) are combined with the component (III). The method (3) in which the contact-treated product of (IV) is brought into contact is preferable, and the method (1) is most preferable. Further, it is preferable that the mixture of the component (I) and the component (II) is brought into contact with the component (III), the component (IV) or the contact-treated product of the component (III) and the component (IV).

In either contact method, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually 6-12 carbon atoms), heptane, hexane, decane and dodecane are generally used in an inert atmosphere such as nitrogen or argon. , A method of contacting each component with stirring or non-stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually 5 to 12 carbon atoms) such as cyclohexane is adopted.
This contact is usually carried out at a temperature of −100 ° C. to 200 ° C., preferably −50 ° C. to 100 ° C., more preferably 0 ° C. to 50 ° C., for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, still more preferably. It is desirable to do it in 30 minutes to 12 hours.
Specific examples of the contact method include a mixture of the component (I) and the component (II), or a liquid in which the component (I) and the component (II) are dissolved or dispersed in the above-mentioned inert solvent, and the component (III). ) Is dissolved or dispersed in an inert solvent, and the obtained mixed solution is mixed with the slurry of the component (IV).

Further, upon contact of the component (I), the component (II), the component (III) and the component (IV), a certain component is soluble or sparingly soluble in an aromatic hydrocarbon solvent, and a certain component is insoluble. Alternatively, either a sparingly soluble aliphatic or alicyclic hydrocarbon solvent can be used.

When the contact reaction between the components is carried out stepwise, the solvent used in the previous stage may be used as it is as the solvent for the contact reaction in the subsequent stage without removing the solvent or the like. In addition, after the contact reaction in the previous stage using a soluble solvent, liquid inert hydrocarbons in which certain components are insoluble or sparingly soluble (for example, pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, xylene, etc.) (Hydrocarbon, alicyclic hydrocarbon or aromatic hydrocarbon) is added to recover the desired product as a solid, or once a part or all of the soluble solvent is removed by means such as drying, which is desired. After the product is taken out as a solid, the subsequent contact reaction of the desired product can also be carried out using any of the above-mentioned inert hydrocarbon solvents. In the present invention, it does not prevent the contact reaction of each component from being carried out a plurality of times.

In the present invention, the ratio of the component (I), the component (II), the component (III) and the component (IV) to be used is not particularly limited, but the following range is preferable.
The molar ratio of component (I) to component (II) (component (I): component (II)) is arbitrarily adjusted to determine the shape of the molecular weight distribution of the resulting polymer, usually 1: 500-500 :. 1, preferably in the range of 1: 100 to 100: 1, more preferably 1:10 to 10: 1.
When an organic aluminum oxy compound is used as the component (III), the molar ratio (Al / M) of the aluminum atom of the organic aluminum oxy compound to the total amount of the transition metal (M) contained in the component (I) and the component (II). Is usually preferably in the range of 1 to 100,000, preferably 5 to 1000, more preferably 50 to 200, and is included in the component (I) and the component (II) when a borane compound or a borate compound is used. The molar ratio (B / M) of the boron atom to the total amount of the transition metal (M) is usually 0. It is desirable to select from 01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10.
Further, when a mixture of an organic aluminum oxy compound, a borane compound and a borate compound is used as the component (III), the transition metal contained in the component (I) and the component (II) is used for each compound in the mixture. It is desirable to select the same usage ratio as above with respect to the total amount of (M).

The amount of the component (IV) used is such that the total amount of the transition metals contained in the component (I) and the component (II) is 0.0001 mmol to 5 mmol, preferably 0.001 mmol to 0.5 mmol per 1 g of the component (IV). More preferably, it is 0.01 mmol to 0.1 mmol.

A catalyst for olefin polymerization can be obtained by contacting the component (I), the component (II), the component (III) and the component (IV) with each other by any of the contact methods (1) to (3). Following the step, the solvent may be removed after performing a washing step to remove unreacted products and unwanted products.
In the washing step, a method of precipitating the catalyst for olefin polymerization, then extracting an unnecessary supernatant liquid and then adding a new solvent to make the stirring uniform, a method of repeating the above-mentioned stirring uniformization, and washing using a filter device. The method of cleaning is used. As the solvent used in the cleaning step, a solvent that can be used in contact with the components (I) to (IV) is used. It is also possible to change the solvent during the cleaning process.
As a step of removing the solvent, a distillation method in which the solvent is evaporated at a pressure corresponding to the boiling point of the solvent, a method in which the solvent is vaporized by a stream of a dry inert gas, or the like can be used. It is desirable to remove the solvent under normal pressure or reduced pressure at 0 ° C. to 200 ° C., preferably 20 ° C. to 150 ° C. for 1 minute to 50 hours, preferably 10 minutes to 10 hours.
The olefin polymerization catalyst obtained after the washing step can be handled or stored in a slurry state, and the olefin polymerization catalyst obtained in the step of removing the solvent can be handled or stored as a powdery solid catalyst.

The catalyst for olefin polymerization can also be obtained by the following method.
Method (4):
The solvent is removed by contacting the component (I) and the component (II) with the component (IV) which is a fine particle carrier, and this is used as a solid catalyst component and is brought into contact with the component (III) which is a co-catalyst under polymerization conditions. ..
Method (5):
The solvent is removed by contacting the component (III) which is a co-catalyst and the component (IV) which is a fine particle carrier, and this is used as a solid catalyst component, which is a catalytically active component (I) and a component (under polymerization conditions). Contact with II).
Also in the case of the above method (4) and the above method (5), the same conditions as described above can be adopted as the component ratio, the contact condition and the solvent removal condition.

Further, a layered silicate can also be used as a component that also serves as a component (III) that is a co-catalyst and a component (IV) that is a fine particle carrier. The layered silicate is a silicate compound having a crystal structure in which planes composed of ionic bonds and the like are stacked in parallel with each other with a weak bonding force. Most layered silicates are naturally produced mainly as the main component of clay minerals, but these layered silicates are not limited to those naturally produced, and may be artificial compounds.
Among these, montmorillonite, saponite, byderite, nontronite, saponite, hectorite, stepnsite, bentonite, teniolite and other smectites, vermiculites and mica are preferred.

In general, natural products are often non-ion exchangeable (non-swellable), in which case they are ion-exchangeable (or swellable) in order to have preferable ion-exchangeable (or swellable) properties. It is preferable to carry out a process for imparting. Among such treatments, the following chemical treatments are particularly preferable. Here, as the chemical treatment, any of a surface treatment for removing impurities adhering to the surface and a treatment for affecting the crystal structure and chemical composition of the layered silicate can be used.
Specifically, (a) acid treatment performed using hydrochloric acid, sulfuric acid, etc., (b) alkaline treatment performed using NaOH, KOH, _NH3 , etc., (c) from Group 2 to Group 14 of the Periodic Table. Salt treatment with salts consisting of at least one anion selected from the group consisting of cations containing at least one selected atom and anions derived from halogen atoms or inorganic acids, (d) alcohol, charcoal. Examples thereof include treatment with organic substances such as hydrogen compounds, formamides and aniline. These processes may be performed alone or in combination of two or more processes.

The particle properties of the layered silicate can be controlled by pulverization, granulation, granulation, separation, etc. at any time before, during, or after all the steps. The method can be arbitrary and purposeful. In particular, regarding the granulation method, for example, a spray granulation method, a rolling granulation method, a compression granulation method, a stirring granulation method, a briquetting method, a compacting method, an extrusion granulation method, and a fluidized bed granulation method. Examples thereof include a method, an emulsified granulation method, and an in-liquid granulation method. Among the above, particularly preferable granulation methods are the spray granulation method, the rolling granulation method and the compression granulation method.

Of course, the above-mentioned layered silicates can be used as they are, but these layered silicates can be used as trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc. It can be used in combination with an organic aluminum compound such as diisobutylaluminum hydride or an organic aluminum oxy compound containing an Al—O—Al bond.

In order to support the catalytically active component (I) and the component (II) on the layered silicate, the component (I) and the component (II) and the layered silicate are brought into mutual contact, or the component (I) and the layered silicate are brought into contact with each other. The component (II), the organoaluminum compound or the organoaluminum oxy compound, and the layered silicate may be brought into contact with each other.
The contact method for each component is not particularly limited, and for example, the following methods can be arbitrarily adopted.
Method (6):
The organoaluminum compound or the organoaluminum oxy compound is brought into contact with the component (I) and the component (II), and then contacted with the layered silicate carrier.
Method (7):
After contacting the component (I) and the component (II) with the layered silicate carrier, they are brought into contact with the organoaluminum compound or the organoaluminum oxy compound.
Method (8):
After contacting the organoaluminum compound or the organoaluminum oxy compound with the layered silicate carrier, the organoaluminum compound or the organoaluminum oxy compound is brought into contact with the component (I) and the component (II).

Among these contact methods, method (6) and method (8) are preferable. In either contact method, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually 6-12 carbon atoms), heptane, hexane, decane and dodecane are generally used in an inert atmosphere such as nitrogen or argon. , A method of contacting each component with stirring or non-stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually 5 to 12 carbon atoms) such as cyclohexane is adopted.
When the component (I) and the component (II) are supported on the layered silicate, the same conditions as those for the above-mentioned inorganic carrier can be adopted as the method of supporting, solvent washing and solvent removal.

The ratio of the components (I) and (II) which are catalytically active components, the organoaluminum compound or the organoaluminum oxy compound, and the layered silicate carrier is not particularly limited, but the following range is preferable.
As for the supported amount of the component (I) and the component (II), the total amount of the transition metal (M) contained in the component (I) and the component (II) is preferably 0.0001 mmol to 5 mmol per 1 g of the layered silicate carrier. Is 0.001 mmol to 0.5 mmol, more preferably 0.01 mmol to 0.1 mmol.
When an organic aluminum compound or an organic aluminum oxy compound is used, the Al atom contained in the organic aluminum compound or the organic aluminum oxy compound is based on the total amount of the transition metal (M) contained in the component (I) and the component (II). The molar ratio (Al / M) is preferably in the range of 0.01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10.

IV. Prepolymerization of the olefin polymerization catalyst The olefin polymerization catalyst thus obtained may be prepolymerized in the polymerization tank or outside the polymerization tank in the presence of the olefin. The olefin refers to a hydrocarbon containing at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, and divinylbenzene. There is no limitation, and a mixture of these and other olefins may be used. Ethylene and propylene are preferable. More preferably, it is ethylene.

The olefin supply method for prepolymerization can be any method such as a supply method for maintaining the olefin in the reaction vessel at a constant speed or a constant pressure state, a combination thereof, and a stepwise change. be.
The prepolymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours. The amount of the prepolymerized polymer is preferably 0.01 parts by weight to 100 parts by weight, more preferably 0.1 parts by weight to 50 parts by weight, based on 1 part by weight of the polyolefin polymerization catalyst. After the prepolymerization is completed, it can be used as it is depending on the usage mode of the catalyst, but it may be dried if necessary.

The prepolymerization temperature is not particularly limited, but is preferably 0 ° C to 100 ° C, more preferably 10 ° C to 70 ° C, particularly preferably 20 ° C to 60 ° C, and even more preferably 30 ° C to 50 ° C. If it falls below this range, the reaction rate may decrease or the activation reaction may not proceed. If it exceeds this range, the prepolymerized polymer may dissolve, or the prepolymerization rate may be too fast and the particle properties may deteriorate. There is a possibility that the active point will be deactivated due to a side reaction.

Prepolymerization can also be carried out in a liquid such as an organic solvent, which is preferred. The concentration of the solid catalyst at the time of prepolymerization is not particularly limited, but is preferably 50 g / L or more, more preferably 60 g / L or more, and particularly preferably 70 g / L or more. The higher the concentration, the more the activation of the component (I) and the component (II) proceeds, and the catalyst becomes a highly active catalyst.

Further, it is also possible to coexist a polymer such as polyethylene, polypropylene or polystyrene or an inorganic oxide solid such as silica or titania in the contact mixture at the time of contact between the catalyst for olefin polymerization and the olefin or after the contact. ..

The catalyst may be dried after the prepolymerization. The drying method is not particularly limited, and examples thereof include vacuum drying, heat drying, and drying by circulating a drying gas. These methods may be used alone or in combination of two or more methods. May be good. In the drying step, the catalyst may be agitated, vibrated, flowed, or allowed to stand.

V. Polymerization of olefins The catalyst for olefin polymerization obtained by the present invention can be used for polymerization of olefins alone or olefins and other comonomer.
The olefin that can be polymerized is preferably one having about 2 to 20 carbon atoms, and specifically, ethylene, propylene, 1-butene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl-1,7. -Octane, cyclopentene, norbornene, ethylidene norbornene and the like can be mentioned. It is preferably an α-olefin having 2 to 8 carbon atoms.

In the case of copolymerization, as the comonomer, an olefin other than the olefin as the main component can be selected and used from those listed as the olefin.
When producing an ethylene-based copolymer, it is preferable to use an α-olefin having 3 to 8 carbon atoms as the olefin comonomer, and it is more preferable to use an α-olefin having 4 to 6 carbon atoms.

As the polymerization mode, any mode can be adopted as long as the catalyst component and each monomer are in efficient contact with each other. Specifically, the slurry method using an inert solvent, the method using propylene as a solvent without substantially using the inert solvent, the solution polymerization method, or the vapor phase in which each monomer is kept in a gaseous state without using a liquid solvent substantially. The law can be adopted. Further, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied. Of these, the slurry method is preferred.
Further, a method of performing multi-step polymerization of two or more steps in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, and polymerization temperature are different from each other is also applied.
In the case of slurry polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as isobutane, hexane, heptane, pentane, cyclohexane, benzene and toluene is used as the polymerization solvent. The polymerization temperature is 0 ° C. to 150 ° C., and hydrogen can be used as an auxiliary as a molecular weight modifier. The polymerization pressure is preferably 0 MPa to 200 MPa, preferably 0 MPa to 6 MPa.
In the case of copolymerization, the amount ratio of each monomer in the reaction system does not have to be constant over time, it is convenient to supply each monomer at a constant mixing ratio, and the mixing ratio of the supplied monomers is set. It is also possible to change it over time. Further, any of the monomers may be added in portions in consideration of the copolymerization reaction ratio.

Generally, when an ethylene polymer is polymerized, in order to suppress static electricity adhesion of the polymer to the polymerization reactor, for example, static electricity such as product name Stadis or product name STATSAFE manufactured by Innospec (distributor Maruwa Bussan) is used. It is also possible to use an inhibitor. As the antistatic agent such as Stadis and STATSAFE, a diluted solution in an inert hydrocarbon medium can be added to the polymerization reactor by a pump or the like.
Examples of the addition method include a method of adding in advance to the catalyst for olefin polymerization and a method of adding to the polymerization reactor, but in the case of slurry polymerization, the addition amount is 0.1 ppm to 500 ppm with respect to the solvent. Is preferable, and 1 ppm to 50 ppm is more preferable. Further, in the case of the vapor phase method, 1 ppm to 500 ppm is preferable, and 10 ppm to 100 ppm is more preferable with respect to the production amount of the ethylene-based polymer per unit time.

The molecular weight of the produced polymer can be adjusted by changing the polymerization temperature, adding hydrogen to the polymerization reactor, or the like, but a method of adjusting by adding hydrogen is preferably used. Hydrogen is inserted into the bond between the transition metal and the polymer chain, causing a chain transfer reaction by hydrogen, and the polymer chain loses the bond with the transition metal and the molecular weight does not become longer. Therefore, if the hydrogen addition amount is increased and the hydrogen concentration in the reactor is increased, the molecular weight is reduced, and if the hydrogen addition amount is decreased and the hydrogen concentration is decreased, the molecular weight is increased.
The likelihood of this hydrogen chain transfer reaction varies with the individual olefin polymerization catalysts and therefore the molecular weight can be controlled by the transition metal compound used. The catalyst for olefin polymerization made from the component (I) used in the present invention is likely to undergo a chain transfer reaction with hydrogen, which is suitable for producing a polymer having a low molecular weight, and conversely for olefin polymerization made from the component (II). The catalyst is suitable for producing a polymer having a high molecular weight because the chain transfer reaction due to hydrogen is unlikely to occur.

The molecular weight distribution of the produced polymer can be controlled by the type of the component (I) and the component (II) and the amount of the component (I) and the component (II) contained in the catalyst for olefin polymerization.
In order to widen the molecular weight distribution, it is possible to control by using a combination of the component (I) and the component (II) such that the difference in the chain transfer reaction by hydrogen becomes large, and the component (I) and the component (II) in the present invention can be controlled. ) Is a suitable combination.
Next, in order to control the shape of the molecular weight distribution, that is, whether there are many low molecular weight polymer components or high molecular weight polymers, it can be controlled by changing the amounts of the component (I) and the component (II).

The density of the produced polymer can be controlled by the concentration in the polymerization reactor of the comonomer used for the copolymerization. When the supply amount of comonomer is increased to increase the concentration in the polymerization reactor, the comonomer incorporated into the monomer chain in the polymer increases, which inhibits the crystallization of the polymer and reduces the density.

In the polymerization, a multi-step polymerization method using a plurality of reactors is also used in addition to using one reactor. It connects reactors with the same or different reaction conditions and feeds the polymer produced in the first reactor with or without solvent to the second reactor continuously or intermittently. The production of the polymer is continued under the second reaction condition. The number of reactors is not limited, but a two- or three-stage reactor is preferably used. Manufactured in each reactor by changing various conditions such as polymerization temperature, polymerization pressure, monomer concentration, comonomer concentration, and hydrogen concentration between the first reaction condition and the second and subsequent reaction conditions. A mixture of polymers is obtained. By changing the hydrogen concentration, it becomes possible to widen the molecular weight distribution, and if the comonomer concentration is changed in addition to the hydrogen concentration, it becomes possible to produce a polymer having a different comonomer content for each molecular weight. Furthermore, it is also possible to control the amount ratio of the polymer produced in each reactor by changing the amount of polymer produced in each reactor by changing the monomer concentration and the polymerization temperature.
In the multi-stage polymerization, a catalyst for olefin polymerization different from or the same as that of the first stage may be added to the second and subsequent stages, or an apparatus for removing unreacted gas may be provided while connecting the reactor. ..

Further, a component for the purpose of removing water, a so-called scavenger, may be added to the polymerization system. The scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, the organoaluminum oxy compound, modified organoaluminum compounds containing branched alkyl, organozinc compounds such as diethylzinc and dibutylzinc, and diethyl. Organoaluminium compounds such as magnesium, dibutylmagnesium and ethylbutylmagnesium, and glinal compounds such as ethylmagnesium chloride and butylmagnesium chloride are used. Among these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferable, and triethylaluminum is particularly preferable.

VI. Physical properties of the obtained olefin-based copolymer By copolymerizing the olefin using the catalyst for olefin polymerization of the present invention, the molecular weight distribution is sufficiently wide, the distribution is widened on the high molecular weight side, and the molecular weight distribution is high. An olefin-based copolymer containing a sufficient amount of branched chains in the molecular weight side region can be produced.
The obtained olefin-based copolymer has high fluidity at the time of melting and high melt strength and extensional viscosity on the high strain side, so that it is not only excellent in moldability, but also has rigidity, strength and durability. It is also excellent in balance and is suitably used as a plastic molding material.
In particular, the ethylene-based copolymer obtained by using the olefin polymerization catalyst of the present invention has not only high fluidity at the time of melting, melt strength and extensional viscosity on the high strain side, but also excellent moldability and rigidity. It is suitably used as a plastic molding material for high-density polyethylene (HDPE) grade applications, which has an excellent balance between strength and durability.
The olefin-based copolymer produced by using the catalyst for olefin polymerization of the present invention may be mixed with another polymer and used. Further, the olefin-based copolymer can be used after being melt-kneaded after mixing various additives in addition to the polymer.

In the present invention, an ethylene-based copolymer having the following physical properties and suitable for high-density polyethylene (HDPE) grade applications can be obtained.
(1) MFR (190 ° C, 2.16 kg load)
The melt flow rate of the ethylene-based polymer obtained in the present invention, that is, MFR (190 ° C., 2.16 kg load) is preferably 0.001 g / 10 min to 1000 g / 10 min, more preferably 0.005 g. It is / 10 minutes to 200 g / 10 minutes, more preferably 0.01 g / 10 minutes to 50 g / 10 minutes, and particularly preferably 0.02 g / 10 minutes to 5.0 g / 10 minutes.

(2) HLMFR (190 ° C. ° C., 21.6 kg load)
The high load melt flow rate of the ethylene polymer obtained in the present invention, that is, HLMFR (190 ° C., 21.6 kg load) is preferably 0.01 g / 10 min to 1000 g / 10 min, more preferably 0. .1 g / 10 minutes to 500 g / 10 minutes, more preferably 1.0 g / 10 minutes to 300 g / 10 minutes, and particularly preferably 2.0 g / 10 minutes to 100 g / 10 minutes.

(3) Density The density of the ethylene-based polymer obtained in the present invention is preferably 0.850 g / cm ³ to 0.980 g / cm ³ , and more preferably 0.935 g / cm ³ to 0.970 g / cm. It is ³ , more preferably 0.945 g / cm ³ to 0.965 g / cm ³ .

(4) Molecular weight distribution (Mw / Mn)
The molecular weight distribution (Mw / Mn) of the ethylene-based polymer obtained in the present invention is preferably 6.0 or more and 60 or less, more preferably 8.0 to 50, still more preferably 10 to 40, and particularly preferably. It is 15 to 25.
In the present invention, the molecular weight distribution (Mw / Mn) is calculated from the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by the gel permeation chromatography (GPC) method.

(5) Ratio of comonomer content on the polymer side to the comonomer content on the low molecular weight side The comonomer on the high molecular weight side of the molecular weight distribution of the olefin polymer with respect to the comonomer content on the low molecular weight side of the molecular weight distribution of the olefin polymer. The content ratio (polymer side comonomer content / low molecular weight side comonomer content) is preferably 4 times or more, more preferably 8 times or more, still more preferably 10 times or more.
In the present invention, the ratio (polymer side comonomer content / low molecular weight side comonomer content) is specified by the following experiment.
[Method for specifying ratio (polymer side comonomer content / low molecular weight side comonomer content)]
A catalyst for olefin polymerization containing component (I), component (III) and (IV) but not component (II), and component (I) containing component (II), component (III) and (IV). A catalyst for olefin polymerization that does not contain the above is prepared, and an olefin-based polymer is produced under the same polymerization conditions using each of these catalysts.
Then, the number of branches contained in the low molecular weight copolymer obtained by using the catalyst containing the component (I) and the high molecular weight copolymer obtained by using the catalyst containing the component (II) are contained. The number of branches is measured and the ratio (polymer side copolymer content / low molecular weight side copolymer content) is calculated.
The value of the obtained ratio is the ratio of the olefin polymer obtained by using the catalyst for olefin polymerization containing the component (I), the component (II), the component (III) and (IV) (containing the polymer side comonomer). Amount / low molecular weight side comonomer content).

(6) Melt tension (MT)
The melt tension (MT) of the ethylene-based polymer obtained in the present invention is preferably 50 mN or more, more preferably 60 mN or more, still more preferably 70 mN or more at a measurement temperature of 190 ° C.
The melting tension can be controlled by MFR or HLMFR. The melt tension can also be adjusted by the molecular weight distribution. When the MFR or HLMFR is reduced, the melt tension is increased, and even if the molecular weight distribution is widened, the melt tension is increased. Further, the melt tension is also affected by the long chain branch, and the larger the amount of the long chain branch, the larger the melt tension. When the melt tension is in the above range, the drawdown resistance is good and molding becomes easy.

(7) Tensile impact strength (TIS)
The tensile impact strength (TIS) of the ethylene-based polymer obtained in the present invention is preferably 100 kJ / m ² or more, more preferably 150 kJ / m ² or more, and further preferably 200 kJ / m ² or more.
In the present invention, the tensile impact strength (TIS) is measured according to the B method of JIS K 7160-1996 using a test piece in the shape of ASTM D1822 Type-S.
The tensile impact strength (TIS) can be controlled by the weight average molecular weight, the molecular weight distribution, and the density. Increasing the molecular weight, narrowing the molecular weight distribution, and decreasing the density lead to an increase in impact strength, but on the other hand, there is a trade-off relationship with formability.

(8) Environmental stress crack resistance The ethylene-based polymer obtained in the present invention has a rupture time of preferably 20 hours or more in the all-around notch type creep test (FNCT) conducted in accordance with ISO 16770, which is more preferable. Is 180 hours or more, more preferably 600 hours or more.
Environmental stress crack resistance also changes mainly with density. Environmental stress crack resistance (FNCT) increases as the comonomer content increases and the density decreases. The influence of the content of comonomer contained in the low molecular weight side is small, but the influence of the content of comonomer contained in the high molecular weight side is large. As the content of comonomer contained in the high molecular weight side increases, the breaking time of FNCT becomes longer. Further, the environmental stress crack resistance is also increased by containing a large amount of high molecular weight components, and when a large amount of high molecular weight components are contained, the fracture time of FNCT becomes long. Therefore, the polymer having a long breaking time is a polymer containing a comonomer on the high molecular weight side and having a sufficient amount of high molecular weight components.

The present invention will be described in more detail in the following Examples and Comparative Examples, but the present invention is not limited thereto.
In the examples, the following evaluation methods were carried out, the catalyst synthesis step and the polymerization step were all carried out in a purified nitrogen atmosphere, and the solvent used was dehydrated with Molecular Sheave 4A (trade name, manufactured by Union Showa Co., Ltd.). The purified product was used.

1. 1. Evaluation method (1) MFR (190 ° C, 2.16 kg load)
The MFR was measured in accordance with JIS K6760 under the conditions of a temperature of 190 ° C. and a load of 2.16 kg.
(2) HLMFR (190 ° C. ° C., 21.6 kg load)
The HLMFR was measured in accordance with JIS K6922-2: 1997 under the conditions of a temperature of 190 ° C. and a load of 21.6 kg.
(3) Density Density was measured according to JIS K6922-1, 2: 1997.

(4) Molecular weight distribution (Mw / Mn)
The gel permeation chromatography (GPC) method was carried out under the conditions shown below, and the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by converting the holding capacity into the molecular weight, and the molecular weight distribution (Mw / Mn) was measured. ) Was calculated.
[GPC device, measurement conditions]
Equipment: Waters GPC (ALC / GPC 150C)
Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm)
Column: Showa Denko AD806M / S (3)
Mobile phase solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Flow rate: 1.0 ml / min Injection amount: 0.2 ml
[Sample preparation]
The sample was dissolved in ODCB (containing 0.5 mg / mL BHT) at 140 ° C. for about 1 hour to prepare a sample solution having a concentration of 1 mg / mL.
[Conversion from retention capacity to molecular weight]
The conversion from the holding capacity to the molecular weight was performed using a calibration curve prepared in advance using standard polystyrene. The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each standard polystyrene is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximating with the least squares method. The following numerical values are used for the viscosity formula [η] = K × Mα used for conversion to the molecular weight.
PS: K = 1.38 × 10 ^-4 , α = 0.7
PE: K = 3.92 × 10 ^-4 , α = 0.733
PP: K = 1.03 × 10 ^-4 , α = 0.78

(5) Measurement of comonomer content and terminal vinyl group content of polymer (NMR analysis)
An ethylene-based polymer produced by using a catalyst containing the component (I) but not the component (II) or a catalyst containing the component (II) but not the component (I) was vacuum-dried at 80 ° C. for 2 hours. After that, it was pressed at 190 ° C. to prepare a press film. About 200 mg of the press film and an ODCB-based mixed solvent were placed in an NMR sample tube and uniformly dissolved with a block heater at 150 ° C. to prepare a sample solution. Using this sample solution, 13C-NMR and 1H-NMR were carried out, and the comonomer content (determined as the number of butyl branches) and the terminal vinyl group content of the ethylene polymer were specified from the measurement results.
[Device]
Equipment: AVANCE400 manufactured by Bruker Japan
Probe: 10mmφ cryoprobe (Type: CP2.1 DUL 400S1 CHD-10 Z XT)
Measurement temperature: 120 ° C
[13C-NMR conditions]
Peak area of 23.3 ppm butyl branch obtained by 1H complete decoupler, 45 ° pulse, uptake time 2.5 seconds, waiting time 0.26 seconds, cumulative 10240-5120 times with 30 ppm -CH2-main chain area The number of butyl branches per 1000 carbon atoms (number of butyl branches / 1000C) was obtained from the divided values.
[1H-NMR condition]
Peak derived from terminal H2C = C (H) -R of 4.8 to 6 ppm obtained by solvent presaturation, 4.5 ° pulse, uptake time 1.8 seconds, waiting time 0.2 seconds, integration 2048 to 1024 times. From the area and the peak area derived from the -CH2-main chain of 1.3 ppm, the number of terminal vinyls per 1000 carbon atoms (number of terminal vinyls / 1000C) was determined.

(6) Molecular weight dependence of comonomer content of polymer (GPC-IR analysis)
GPC-IR measurement was carried out on the ethylene-based polymer produced by using the catalyst containing the component (I) and the component (II), and the correlation between the transition of the molecular weight and the number of short chain branches derived from the comonomer was observed. The following devices and conditions for GPC-IR are as follows.
[Device]
Equipment: Plymer Char GPC-IR detector: IR-6
Column: Showa Denko HT-806M (2)
Mobile phase solvent: o-dichlorobenzene (3.6 g / 18 L of trimethylphenol added as an antioxidant)
Measurement temperature: 145 ° C Flow rate: 1.0 ml / min Injection amount: 20 μL
[Sample preparation]
The sample was dissolved in a vial at a concentration of about 1 mg / ml and used for measurement.
The calibration curve was made of standard polystyrene and converted to polyethylene using the Q factor. The Q factor used was -0.3649, which was included in the Playmer Char software by default. As the standard polystyrene used, a sample set of Showdex Standard SM-105 (trade name, manufactured by Showa Denko KK), n-eicosane, and n-tetracontane were used. The molecular weights of n-icosane and n-tetracontane were converted to polystyrene using a Q factor.

(7) Melt tension (MT)
It was determined by measuring the stress when the molten ethylene polymer was stretched at a constant speed, and was measured under the following conditions.
[Measurement condition]
Model used: Capillograph 1B manufactured by Toyo Seiki Seisakusho
Nozzle diameter: 2.095 mm
Nozzle length: 8.0 mm
Inflow angle: 180 ° (flat)
Extrusion speed: 15 mm / min
Pick-up speed: 6.5m / min
Measurement temperature: 190 ° C

(8) Tensile impact strength (TIS)
[Method for preparing tensile impact strength test sample]
The sample is placed in a 1 mm thick heating press mold, preheated in a hot press machine with a surface temperature of 230 ° C. for 5 minutes, and then pressurized and depressurized repeatedly to melt the sample and degas the residual gas in the sample. Then, the pressure was further increased at 4.9 MPa, and the mixture was held for 5 minutes. Then, it was gradually cooled at a rate of 10 ° C./min under a pressure of 4.9 MPa, and when the temperature dropped to around room temperature, the molded plate was taken out from the mold. The state of the obtained molded plate was adjusted for 48 hours or more in an environment of a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5 ° C. A test piece in the shape of ASTM D1822 Type-S was punched out from the press plate after adjusting the state to prepare a tensile impact strength test sample.
[Tensile Impact Strength Test Conditions (TIS)]
Using the above test piece, the tensile impact strength was measured according to the B method of JIS K 7160-1996. The only difference from JIS K 7160-1996 is the shape of the test piece. Regarding other measurement conditions, the test was carried out by a method according to JIS K 7160-1996.

(9) Environmental stress crack resistance (FNCT)
An all-around notch creep test (FNCT) was performed according to ISO 16770. For the sample, a 1 mm notch was made with a razor blade around the entire circumference of a prism having a size of 6 mm × 6 mm × 11 mm, and a test piece having a cross section having a size of 4 mm × 4 mm was prepared, and pure water at 80 ° C. was prepared. Among them, a tensile stress corresponding to 3.7 MPa was applied to the test piece, and the time until the test piece broke was measured and used as the fracture time of FNCT.

2. 2. Synthesis example of component (I) and component (II) [Synthesis example 1]
Synthesis of {o-xylene-α, α'-bis- (η5-1-indenyl) -zirconium} dichloride (hereinafter abbreviated as metallocene I-1):
Metallocene I-1 is compound number 5 in Table 1 above. Metallocene I-1 was synthesized with reference to Example 1 of JP-A-9-286812 and the synthesis example of compound 1a described in Journal of Organometallic Chemistry 535 (1997) 29-32.

[Synthesis Example 2]
Synthesis of {3,4-dimethyl-o-xylene-α, α'-bis- (η5-1-indenyl) -zirconium} dichloride (hereinafter abbreviated as metallocene I-2):
(2-1) Synthesis of 3,4-dimethyl-α, α'-dichloro-o-xylene In a 500 ml flask, 10.00 g (0.09419 mol) of o-xylene and 94.20 ml (0.9487 mol) of concentrated hydrochloric acid were placed. In addition, it was cooled to 0 ° C. To this, 8.55 g (0.0377 mol) of 1-butyl-3-methylimidazolium tetrafluoroborate and 8.56 g (0.283 mol) of paraformaldehyde were added, and the mixture was stirred at 70 ° C. for 12 hours. 94.20 ml (0.9487 mol) of concentrated hydrochloric acid and 2.85 g (0.0942 mol) of paraformaldehyde were added again, and the mixture was further stirred at 70 ° C. for 12 hours. The reaction mixture was concentrated by distillation under reduced pressure, 200 ml of distilled water was added, and extraction was performed 3 times with 200 ml of dichloromethane. The obtained organic phase was washed with 200 ml of distilled water and dried over anhydrous sodium sulfate. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified on a silica gel column (petroleum ether). 18.00 g of white powder of 3,4-dimethyl-α, α'-dichloro-o-xylene (yield 94). %) Was obtained.

(2-2) Synthesis of α, α'-bis- (1-indenyl) -3,4-dimethyl-o-xylene To a 500 ml flask, 17.16 g (0.1477 mol) of indene and 200 ml of THF were added, and the temperature was −78 ° C. Cooled down to. 55.14 ml (0.1379 mol) of an n-butyllithium / n-hexane solution (2.5 M) was added dropwise thereto, and the mixture was returned to room temperature and stirred for 2 hours. The mixture was cooled to −78 ° C. again, a solution of 10.00 g (0.049223 mol) of 3,4-dimethyl-α, α'-dichloro-o-xylene in 50 ml of THF was added dropwise, and the mixture was stirred overnight while gradually returning to room temperature. The reaction was slowly poured into 200 ml of distilled water and extracted 3 times with 250 ml of dichloromethane. The obtained organic phase was washed with 120 ml of saturated brine and dried over anhydrous sodium sulfate. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified on a silica gel column (petroleum ether / ethyl acetate = 10/1), α, α'-bis- (1-indenyl) -3,4-dimethyl-. 12.00 g (yield 67%) of o-xylene yellow oil was obtained.

(2-3) {3,4-dimethyl-o-xylene-α, α'-bis- (η5-1-indenyl) -zirconium} Synthesis of dichloride In a 200 ml flask, α, α'-bis- (1-) Indenyl) -3,4-dimethyl-o-xylene 1.99 g (5.49 mmol) and 60 ml of THF were added, and the mixture was cooled to −78 ° C. 7.20 ml (11.4 mmol) of an n-butyllithium / n-hexane solution (1.58 M) was added dropwise thereto, and the mixture was returned to room temperature and stirred for 3 hours. A separately prepared solution of 1.54 g (6.61 mmol) of zirconium tetrachloride / 10 ml of n-hexane / 40 ml of THF was added thereto at 0 ° C., and the mixture was stirred overnight while gradually returning to room temperature. A yellow powder was obtained by distilling off the solvent from the reaction solution under reduced pressure. Toluene (35 ml) was added to this powder at room temperature, and the mixture was stirred for 30 minutes. The insoluble matter was removed by filtration, and the solvent was distilled off under reduced pressure from the obtained filtrate to obtain a yellow powder again. The obtained yellow powder was recrystallized from a mixed solvent of dichloromethane / n-hexane, and {3,4-dimethyl-o-xylene-α, α'-bis- (η5-1-indenyl) -zylconyl} dichloride yellow. 0.284 g of powder (yield 10%) was obtained.
^{1 1} H-NMR value (CDCl ₃ ): δ2.35 (s, 6H), δ3.99 (d, 2H), δ4.13 (d, 2H), δ5.97 (d, 2H), δ6.01 ( d, 2H), δ7.12 (dd, 2H), δ7.19 (s, 2H), δ7.31 (dd, 2H), δ7.42 (d, 2H), δ7.64 (d, 2H).

[Synthesis Example 3]
Synthesis of {o-xylene-α, α'-bis- (η5- (5,6-dimethyl) -1-indenyl) -zirconium} dichloride (hereinafter abbreviated as metallocene I-3):
It was synthesized according to the procedure described in Example 7 of JP-A-9-286812.

[Synthesis Example 4]
Bis (n-butylcyclopentadienyl) zirconium dichloride (hereinafter abbreviated as metallocene I-4) was obtained from Fuji Film Wako Pure Chemical Industries, Ltd.

[Synthesis Example 5]
{Synthesis of racemic-dimethylsilylenebis (2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl) zirconium} dichloride (hereinafter abbreviated as metallocene II-1):
Metallocene II-1 is a compound represented by the above formula (2-1). A ligand was synthesized according to the procedure described in Synthesis Example 1 of Japanese Patent Application No. 2011-008562, and metallocene II-1 was synthesized using zirconium tetrachloride instead of hafnium tetrachloride.

[Synthesis Example 6]
Synthesis of racemic-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride (hereinafter abbreviated as metallocene II-2):
Metallocene II-2 is described in Organometallics, 1994, vol. 13, pp. It was synthesized according to the procedure described in 954-963.

[Synthesis Example 7]
{Synthesis of diphenylmethylene (3-methyl-1-cyclopentadienyl) (2,7-dit-butyl-9-fluorenyl)} zirconium dichloride (hereinafter abbreviated as metallocene II-3):
Metallocene II-3 was synthesized according to the procedure described in Manufacturing Example 2 of US2015 / 0299352A1.

3. 3. Preparation of catalyst and production of ethylene-based polymer [Example 1]
(1) Preparation of solid catalyst 38 ml of toluene was added to 3.8 g of silica gel obtained by calcining an uncalcined product of siropol 2212 manufactured by Grace Co., Ltd. at 400 ° C. for 7 hours to form a slurry at 40 ° C. to prepare the component (IV) in advance.
Separately from the above steps, 25 ml of toluene and methyl as component (III) are placed in a container weighing 28 mg (58 μmol) of metallocene I-1 as component (I) and 32 mg (38 μmol) of metallocene II-1 as component (II). 10 ml (30 mmol as aluminum) of an alminoxane toluene solution (purchased from Albemarle; MAO concentration 20 wt%) was added, and the mixture was stirred at room temperature for 1 hour. The total amount of metallocene I-1 and metallocene II-1 per 1 g of silica gel is 25 μmol / g.
This solution was added to the toluene slurry of silica gel, which is the component (IV). Then, after stirring at 40 ° C. for 1 hour, the solvent was distilled off under reduced pressure to obtain a pink smooth solid catalyst (MIX-1).

(2) Ethylene / hexene copolymer A ethylene / 1-hexene copolymer was produced using the solid catalyst (MIX-1) obtained in (1) above.
That is, in a stainless steel autoclave with an internal volume of 2 liters equipped with a stirring and temperature control device, 1.0 mmol of triisobutylaluminum and 2 ml of 1-hexane under nitrogen, a product of Ino-Spec Co., Ltd. as a stain inhibitor for the reactor. 1 ml of the name Statsafe 6000 diluted to 2 vol% with hexane and 800 ml of purified isobutane were added, and the temperature was raised to 70 ° C. with stirring. Then, after introducing 15 ml (0.67 mmol) of hydrogen, ethylene was introduced until the partial pressure reached 1 MPa. Then, 50 mg of the solid catalyst (MIX-1) was press-fitted with nitrogen gas to carry out polymerization for 60 minutes. During the polymerization, the temperature was controlled so as to maintain 70 ° C., and ethylene was continuously supplied so that the total pressure became constant.
During the polymerization reaction, 1-hexene and hydrogen were also supplied in proportion to the ethylene consumption rate. As a result, the molar ratio of hydrogen to ethylene in the gas phase of the autoclave before the start of the polymerization was 0.09 mol%, whereas it was maintained at 0.1 mol% at the end of the polymerization. The amount of 1-hexene added during the polymerization was 2 ml, which was 0.9 wt% with respect to the produced polyethylene.
As a result of the polymerization, 142 g of free-flowing polyethylene was produced. The polymerization results are summarized in Table 2. The results of GPC-IR of the obtained polyethylene are shown in FIG.
By combining metallocene I-1 and metallocene II-1, it can be seen that the molecular weight distribution is wide and the comonomer is preferentially introduced to the high molecular weight side.

[Comparative Example 1a]
A solid catalyst (SI-1) was produced in the same manner as in Example 1 except that 25 μmol of metallocene I-1 was used with respect to 1 g of silica gel instead of using metallocene I-1 and metallocene II-1. Ethylene / hexene copolymerization was carried out. The results are summarized in Table 2.
[Comparative Example 1b]
A solid catalyst (SII-1) was produced in the same manner as in Example 1 except that 25 μmol of metallocene II-1 was used with respect to 1 g of silica gel instead of using metallocene I-1 and metallocene II-1. Ethylene / hexene copolymerization was carried out. The results are summarized in Table 2.

[Example 2]
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 30 mg (58 μmol) of metallocene I-2 was used instead of metallocene I-1 as the component (I), and the solid catalyst MIX-2 was used. Obtained.
(2) Ethylene / hexene copolymerization Next, ethylene / hexene copolymerization was carried out in the same manner as in Example 1 using 55 mg of MIX-2. The molar ratio of hydrogen to ethylene in the gas phase of the autoclave before the start of the polymerization was 0.08 mol%, whereas it was maintained at 0.1 mol% at the end of the polymerization. The amount of 1-hexene added during the polymerization was 2 ml, which was 1.0 wt% with respect to the produced polyethylene.
As a result of the polymerization, 139 g of free-flowing polyethylene was produced. The polymerization results are summarized in Table 2.

[Comparative Example 2a]
A solid catalyst (SI-2) was produced in the same manner as in Example 1 except that 25 μmol of metallocene I-2 was used with respect to 1 g of silica gel instead of using metallocene I-1 and metallocene II-1. Similarly, ethylene / hexene copolymerization was carried out. The results are summarized in Table 2.

[Example 3]
(1) Preparation of solid catalyst Except that the amount of metallocene I-3 used as component (I) was 42 mg (76 μmol) instead of metallocene I-1, and the amount of metallocene II-1 used as component (II) was 16 mg (19 μmol). , A solid catalyst was prepared in the same manner as in Example 1 to obtain a solid catalyst MIX-3.
(2) Ethylene / hexene copolymerization Next, ethylene / hexene copolymerization was carried out in the same manner as in Example 1 except that 53 mg of MIX-3 and 1 ml of 1-hexene were used. The molar ratio of hydrogen to ethylene in the gas phase of the autoclave before the start of the polymerization was 0.12 mol%, whereas it was 0.06 mol% at the end of the polymerization. The amount of 1-hexene added during the polymerization was 1 ml, which was 0.5 wt% with respect to the produced polyethylene.
As a result of the polymerization, 134 g of free-flowing polyethylene was produced. The polymerization results are summarized in Table 2.

[Comparative Example 3a]
A solid catalyst (SI-3) was produced in the same manner as in Example 1 except that 25 μmol of metallocene I-3 was used with respect to 1 g of silica gel instead of using metallocene I-1 and metallocene II-1. Similarly, ethylene / hexene copolymerization was carried out. The results are summarized in Table 2.

[Example 4]
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 24 mg (38 μmol) of metallocene II-2 was used instead of metallocene II-1 as the component (II), and the solid catalyst MIX-4 was used. Obtained.
(2) Ethylene / hexene copolymerization Next, ethylene / hexene copolymerization was carried out in the same manner as in Example 1 except that 55 mg of MIX-4 was used. The molar ratio of hydrogen to ethylene in the gas phase of the autoclave before the start of the polymerization was 0.07 mol%, whereas it was 0.06 mol% at the end of the polymerization. The amount of 1-hexene added during the polymerization was 2 ml, which was 1.1 wt% with respect to the produced polyethylene.
As a result of the polymerization, 119 g of free-flowing polyethylene was produced. The polymerization results are summarized in Table 2.
(3) Evaluation of Physical Properties of Copolymer The obtained ethylene / hexene copolymer was measured for molecular weight distribution, MT, TIS, and FNCT. The results are summarized in Table 4. The results of GPC-IR of the obtained polyethylene are shown in FIG.

[Comparative Example 4b]
A solid catalyst (SII-2) was produced in the same manner as in Example 1 except that 25 μmol of metallocene II-2 was used with respect to 1 g of silica gel instead of using metallocene I-1 and metallocene II-1. Similarly, ethylene / hexene copolymerization was carried out. The results are summarized in Table 2.

[Example 5]
(1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1 except that 26 mg (38 μmol) of metallocene II-3 was used instead of metallocene II-1 as the component (II), and the solid catalyst MIX-5 was used. Obtained.
(2) Ethylene / hexene copolymerization Next, ethylene / hexene copolymerization was carried out in the same manner as in Example 1 except that 52 mg of MIX-5 was used. The molar ratio of hydrogen to ethylene in the gas phase of the autoclave before the start of the polymerization was 0.09 mol%, whereas it was 0.08 mol% at the end of the polymerization. The amount of 1-hexene added during the polymerization was 2 ml, which was 0.9 wt% with respect to the produced polyethylene.
As a result of the polymerization, 145 g of free-flowing polyethylene was produced. The polymerization results are summarized in Table 2.

[Comparative Example 5b]
A solid catalyst (SII-3) was produced in the same manner as in Example 1 except that 25 μmol of metallocene II-3 was used with respect to 1 g of silica gel instead of using metallocene I-1 and metallocene II-1. Then, ethylene / hexene copolymerization was carried out in the same manner as in Example 1 except that 15 ml (0.67 mmol) of hydrogen was changed to 50 ml (2.2 mmol). The results are summarized in Table 2.
When polymerized with SII-3 at the same hydrogen concentration as in Example 1, polyethylene that did not flow was obtained. Therefore, the hydrogen concentration was increased.

[Example 6]
(1) Preparation of solid catalyst Example 1 except that the amount of metallocene I-1 used as the component (I) was 34 mg (68 μmol) and the amount of the metallocene II-1 used as the component (II) was 19 mg (23 μmol). A solid catalyst was prepared in the same manner to obtain a solid catalyst MIX-6.
(2) Ethylene / hexene copolymerization Next, ethylene / hexene copolymerization was carried out in the same manner as in Example 1 except that 31 mg of MIX-6 was used and the amount of hydrogen was 30 ml (1.3 mmol). The molar ratio of hydrogen to ethylene in the gas phase of the autoclave before the start of the polymerization was 0.18 mol%, whereas it was 0.13 mol% at the end of the polymerization. The amount of 1-hexene added during the polymerization was 1 ml, which was 0.9 wt% with respect to the produced polyethylene.
As a result of the polymerization, 78 g of free-flowing polyethylene was produced.
(3) Evaluation of Physical Properties of Copolymer The obtained ethylene / hexene copolymer was measured for molecular weight distribution, MT, TIS, and FNCT. The results are summarized in Table 4.

[Example 7]
(1) Preparation of solid catalyst Example 1 except that the amount of metallocene I-1 used as the component (I) was 32 mg (65 μmol) and the amount of metallocene II-1 used as the component (II) was 19 mg (30 μmol). A solid catalyst was prepared in the same manner to obtain a solid catalyst MIX-7.
(2) Ethylene / hexene copolymerization Then, using 42 mg of MIX-7, the polymerization was carried out at 25 ml (1.1 mmol) of hydrogen at 90 ° C. for 0.9 hours in the same manner as in Example 1. Ethylene / hexene. Copolymerization was performed. The molar ratio of hydrogen to ethylene in the gas phase of the autoclave before the start of the polymerization was 0.14 mol%, whereas it was 0.09 mol% at the end of the polymerization. The amount of 1-hexene added during the polymerization was 2 ml, which was 0.9 wt% with respect to the produced polyethylene.
As a result of the polymerization, 150 g of free-flowing polyethylene was produced.
(3) Evaluation of Physical Properties of Copolymer The obtained ethylene / hexene copolymer was measured for molecular weight distribution, MT, TIS, and FNCT. The results are summarized in Table 4. The results of GPC-IR of the obtained polyethylene are shown in FIG.

[Comparative Example 6]
(1) Preparation of solid catalyst 23 mg (58 μmol) of metallocene I-4 instead of metallocene I-1 as component (I), and 24 mg (38 μmol) of metallocene II-2 instead of metallocene II-1 as component (II). A solid catalyst was prepared in the same manner as in Example 1 except that it was used, and a solid catalyst MIX-8 was obtained.
(2) Ethylene / hexene copolymerization Next, using 53 mg of MIX-8, carry out ethylene / hexene copolymerization in the same manner as in Example 1 except that hydrogen was added to 38 ml (1.7 mmol) and 1-hexene was added to 1 ml. went. The molar ratio of hydrogen to ethylene in the gas phase of the autoclave before the start of the polymerization was 0.19 mol%, whereas it was 0.11 mol% at the end of the polymerization. The amount of 1-hexene added during the polymerization was 1 ml, which was 0.5 wt% with respect to the produced polyethylene.
As a result of the polymerization, 130 g of free-flowing polyethylene was produced.
(3) Evaluation of Physical Properties of Copolymer The obtained ethylene / hexene copolymer was measured for molecular weight distribution, MT, TIS, and FNCT. The results are summarized in Table 4.

[Comparative Example 7]
Physical properties of Evolu H SP6505 (medium- and high-density polyethylene obtained by a slurry method multi-stage polymerization process using a metallocene catalyst, manufactured by Prime Polymer Co., Ltd.) were measured, and the results are summarized in Table 4.

[Comparative Example 8]
Table 4 summarizes the results of physical property measurements for the product name Novatec HD HB431 (high-density polyethylene manufactured by Japan Polyethylene Corporation).

[Reference example]
The following is an example carried out to show the characteristics of the transition metal compound used in the examples. It can be seen that the ratio of the number of butyl branches is as high as 13 times due to the combination of metallocene I-1 and metallocene II-1.
[Reference Example 1]
Ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1 except that 1-hexene was adjusted to 6 ml using the solid catalyst SI-1. The number of butyl branches and the number of terminal vinyls were determined by NMR analysis of the obtained polyethylene. The results are summarized in Table 3.
[Reference Example 2]
Ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1 except that 1-hexene was adjusted to 6 ml using the solid catalyst SII-1. The number of butyl branches and the number of terminal vinyls were determined by NMR analysis of the obtained polyethylene. The results are summarized in Table 3.

[Reference Example 3]
Ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1 except that 1-hexene was adjusted to 6 ml using the solid catalyst SI-2. The number of butyl branches and the number of terminal vinyls were determined by NMR analysis of the obtained polyethylene. The results are summarized in Table 3.
[Reference example 4]
Ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1 except that 1-hexene was adjusted to 6 ml using the solid catalyst SI-3. The number of butyl branches and the number of terminal vinyls were determined by NMR analysis of the obtained polyethylene. The results are summarized in Table 3.
[Reference Example 5]
Ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1 except that the solid catalyst SII-2 was used to make 75 ml (3.3 mmol) of hydrogen and 6 ml of 1-hexene. The number of butyl branches and the number of terminal vinyls were determined by NMR analysis of the obtained polyethylene. The results are summarized in Table 3.
[Reference Example 6]
Ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1 except that hydrogen was 70 ml (3.1 mmol) and 1-hexene was 6 ml using the solid catalyst SII-3. The number of butyl branches and the number of terminal vinyls were determined by NMR analysis of the obtained polyethylene. The results are summarized in Table 3.

(* 1) Polymerization activity unit: g / g / h / MPa (partial pressure of ethylene)
The polymerization activity is 1 g of a solid catalyst, a polymerization time of 1 hour, and a polymer production amount (unit: g) per 1 MPa of ethylene partial pressure.
(* 2) An average value (unit: mol%) obtained by gas analysis of the gas phase portion of the reactor during polymerization.

4. Consideration From Comparative Examples 1a and 1b in Table 2, it can be seen that when the component (I) or the component (II) is used alone as the catalytically active ingredient, the molecular weight distribution of the obtained ethylene polymer is narrow.
On the other hand, in Example 1, it can be seen that the molecular weight distribution of the ethylene-based polymer obtained by combining metallocene I-1 and metallocene II-1 is wide. Similarly, Example 2 for Comparative Example 2a and Comparative Example 1b, Example 3 for Comparative Example 3a and Comparative Example 1b, Example 4 for Comparative Example 1a and Comparative Example 4b, and Example 5 for Comparative Example 1a and Comparative Example 5b. It can be seen that the molecular weight distribution is widening in.

FIG. 1 shows the results of GPC-IR analysis of Example 1. SCB (Short Chain Branch) means the number of short chain branches obtained from the strength of ₃ CH groups detected by IR analysis, and in the case of this example, the number of carbon atoms produced by copolymerizing the comonomer hexene. The number of branched chains of 4 is shown. It should be noted that the reason why the SCB is large in the region where LogM <4 is included is that an error due to the detection of the _three polyethylene molecule terminal CHs is included, and the SCB is not really large.
In FIG. 1, the low molecular weight polyethylene having a peak of logM of 4.5 is generated from the catalytic reaction of the solid catalyst (SI-1) containing the metallocene I-1 of the component (I), and the logM is 5. It is considered that the high molecular weight polyethylene having a peak of 9 is generated from the catalytic reaction of the solid catalyst (SII-1) containing the metallocene II-1 of the component (II).
When the SCB at each peak is read, the SCB derived from metallocene I-1 is almost 0, and the SCB derived from metallocene II-1 is 2.5. Assuming that the SCB derived from metallocene I-1 is estimated to be 0.1 at most, the ratio of the hexene content (ratio of SCB) between the high molecular weight side region and the low molecular weight side region of polyethylene obtained in Example 1 is. It is a high value of 2.5 / 0.1 = 25 times, and by combining the component (I) and the component (II), it is possible to introduce a high degree of comonomer on the high molecular weight side of the olefin polymer. Is shown. Examples of similar analysis results are shown in FIGS. 2 and 3, respectively, for Example 4 and Example 7. It can be seen that in each case, the comonomer can be highly introduced on the high molecular weight side.

The number of butyl branches in Table 3 means the number of branched chains having 4 carbon atoms produced by copolymerizing hexene, which is a comonomer.
When the metallocene II-1 used as the component (II) in Example 1 and the metallocene I-1 used as the component (I) are used alone and the copolymerization of ethylene / 1-hexene is carried out under the same polymerization conditions. In the copolymer derived from metallocene II-1, the number of butyl branches was 5.1, whereas in the copolymer derived from metallocene I-1, the number of butyl branches was 0.4 / 1000C. That is, the ratio (polymer side comonomer content / low molecular weight side comonomer content) was calculated to be 5.1 / 0.4 = 13, indicating a difference of 13 times.
From the above results, it can be seen that in Example 1, by combining metallocene I-1 and metallocene II-1, the molecular weight distribution is wide and the comonomer is preferentially introduced to the high molecular weight side. As described above, the characteristics of the component (II) and the component (I) are similarly shown in Reference Examples 3 to 6 in Table 3, and the combination of the component (I) and the component (II) of the present application can be used. It can be seen that it is a combination that can highly introduce comonomer on the high molecular weight side.
Table 4 compares the physical characteristics of the obtained polyethylene. Comparative Example 6 uses non-crosslinked metallocene as the component (I), and although the molecular weight distribution is the same and the HLMFR is almost the same as that of Example 4, the intensity, FNCT, and MT are all low. Comparative Example 7 is polyethylene obtained by two-stage polymerization using a metallocene catalyst, which has high strength and sufficiently high FNCT, but has low MT and therefore poor moldability. Comparative Example 8 is a commercially available HDPE grade, and Examples 4, 6 and 7 are superior in strength, FNCT, and MT.

By copolymerizing the olefin using the olefin polymerization catalyst component of the present invention and the olefin polymerization catalyst, the molecular weight distribution is sufficiently wide, the distribution is widened on the high molecular weight side, and the high molecular weight distribution is on the high molecular weight side. Since it is possible to produce an olefin-based polymer containing a sufficient amount of branched chains in the region, it is used for producing an olefin-based copolymer having an excellent balance between formability, rigidity, strength and durability. In particular, it can be suitably used for producing an ethylene-based copolymer suitable for high-density polyethylene (HDPE) grade applications.

Claims (11)

A catalyst component for olefin polymerization, which comprises the following component (I) and component (II).
[Component (I)]
Transition metal compound represented by the following formula (1)

[During the ceremony,
M ¹ represents a transition metal of Group 4 of the periodic table.
L ¹ and L ² represent a ligand containing a cyclopentadienyl structure and are coordinated to M ¹ .
Each of X ¹ and X ² independently has a hydrogen atom, a halogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon containing an oxygen atom or a nitrogen atom. A hydrocarbon group having a number of 3 to 20 or a hydrocarbon group substituted amino group having a carbon number of 1 to 20 is shown.
J ¹ and J ² represent carbon atoms.
A ¹ and A ² indicate a cross-linking group that binds J ¹ and L ¹ and J ² and L ² , respectively, and are selected from the following groups.
-CR ³ _2- , -SiR ³ _2- , -NR ^3- , -PR ^3- , -O-, -S-, [Here, R ³ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Two ^R3s may combine to form a cyclic structure],
R ¹ and R ² independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a hydrocarbon having 1 to 20 carbon atoms including 1 to 6 silicon atoms. A hydrogen group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms is shown. R ¹ and R ² may combine with each other to form a cyclic structure with J ¹ and J ² . ]
[Ingredient (II)]
Transition metal compound selected from the compound group represented by the following formula (2), formula (3) or formula (4) Formula (2):
A ³ _q L ³ L 3'M ³ X ³ X ^{3 '}
[During the ceremony,
M ³ indicates a transition metal of Group 4 of the periodic table.
L ³ and L ^{3'independently} represent ligands containing a cyclopentadienyl structure and are coordinated to M ³ . The ligand containing the cyclopentadienyl structure has a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms containing 1 to 6 silicon atoms. Substituted with a hydrocarbon group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group substituted silyl group having 1 to 20 carbon atoms. It may have been. If adjacent substituents are present on L ³ or L ^3' , they may be combined to form a ring structure.
X ³ and X ^3'contain a hydrogen atom ^, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom independently of each other. A hydrocarbon group having 3 to 20 carbon atoms or a hydrocarbon group substituted amino group having 1 to 20 carbon atoms is shown.
A ³ indicates a cross-linking group that crosslinks L ³ and L ^3' , and may or may not be present, and if present, has a cross-linking structure between L ³ and L ^3' .
q is 0 or ¹ and indicates the number of A3. ]
Equation (3):
A ⁴ L ⁴ M ⁴ X ⁴ X ^4'
[During the ceremony,
M ⁴ indicates a transition metal of Group 4 of the periodic table.
L ⁴ represents a ligand containing a cyclopentadienyl structure and is coordinated to M ⁴ . The ligand containing the cyclopentadienyl structure has a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms containing 1 to 6 silicon atoms. Substituted with a hydrocarbon group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group substituted silyl group having 1 to 20 carbon atoms. It may have been.
^X4 and ^{X4'independently} form a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom, which are bonded to the metal ^M4 , respectively. A hydrocarbon group having 3 to 20 carbon atoms or a hydrocarbon group substituted amino group having 1 to 20 carbon atoms is shown.
A ⁴ represents an organic group having a hetero atom bonded to L ⁴ , and is bonded to M ⁴ via the hetero atom. ]
Equation (4):
L ⁵ _m M ⁵ X ⁵ _p
[During the ceremony,
M ⁵ indicates a transition metal of Group 3 to 11 of the Periodic Table.
The m ^L5s each independently represent a hydrocarbon group substituted with a substituent having an atom selected from two or more oxygen, nitrogen, phosphorus, and sulfur atoms, and at least two of the oxygen. , Nitrogen, phosphorus, and an atom selected from sulfur atoms are bonded to ^M5 .
Each of the p ^X5s has a hydrogen atom, a halogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon containing an oxygen atom or a nitrogen atom, which independently bond with M5. The number 3 to 20 hydrocarbon groups or neutral Lewis bases are shown.
m represents the number of L5 and is ¹ or 2.
p indicates the number of X, which is the number selected so that the transition metal compound of the formula (4) is electrically neutral. ] The catalyst component for olefin polymerization according to claim 1, wherein the component (I) has a cyclic structure in which R ¹ , R ² , J ¹ and J ² are formed in the formula (1). The catalyst component for olefin polymerization according to claim 2, wherein the component (I) is a transition metal compound represented by any of the following formulas (1-1) to (1-5).

[During the ceremony,
M ¹ , L ¹ , L ² , X ¹ , X ² , J ¹ , J ² , A ¹ and A ² are the same as those in the above formula (1).
^R4 indicates a substituent existing on the 6-membered ring, and may or may not be present. If present, each of them independently has a halogen atom, a hydrocarbon group having 1 to 9 carbon atoms, and carbon. An alkoxy group having a number of 1 to 9, a halogen-substituted hydrocarbon group having 1 to 9 carbon atoms, a hydrocarbon group having 3 to 9 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, and a hydrocarbon group having 1 to 9 carbon atoms. It is an amino group that may be substituted with a silyl group or a hydrocarbon group having 1 to 9 carbon atoms. R ⁴ may form a crosslinked structure in the 6-membered ring in which the R ⁴ is present. When two or more R ^4s are present, they may be bonded to form a fused ring that shares a part of the constituent atoms of the 6-membered ring in which the R ⁴ is present, or a substituent may be formed on the condensed ring. May have.
n indicates the number of ^R4 existing on the 6-membered ring, and indicates 0 to 4. ] The catalyst component for olefin polymerization according to any one of claims 1 to 3, wherein the component (II) is a transition metal compound represented by the formula (2). The component (II) is a combination in which q is 1 and L ³ and L ^3'are both ligands having an indenyl skeleton in the formula (2), and one has a cyclopentazinyl skeleton. It is a transition metal compound having a combination selected from a combination of a ligand and the other being a ligand having a fluorenyl skeleton and a combination of both being a ligand having a fluorenyl skeleton. The catalyst component for olefin polymerization according to claim 4. In the formula (2), the component (II) has q of 1, and L ³ and L 3'are both ligands having an indenyl skeleton, and at least one of L ³ and L ^{3' .} The ligand having an indenyl skeleton of is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a frill group which may have a substituent or a substituent at the position of the 2-position of the indenyl skeleton. The catalyst component for olefin polymerization according to claim 5, wherein the transition metal compound has a thienyl group which may have a group. In the formula (2), the component (II) has q of 1, and L ³ and L 3'are both ligands having an indenyl skeleton, and at least one of L ³ and L ^{3' .} The ligand having an indenyl skeleton of is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a frill group which may have a substituent, or a frill group at the 2-position position of the indenyl skeleton. The claim is a transition metal compound having a thienyl group which may have a substituent and further having an aryl group which may have a substituent at the position of the 4-position of the indenyl skeleton. 6. The catalyst component for olefin polymerization according to 6. The catalyst component for olefin polymerization according to claim 7, wherein the component (II) is a transition metal compound represented by the following formula (2-1).

[During the ceremony,
M ³ represents a titanium atom, a zirconium atom or a hafnium atom.
X ³ and X ^3'are the same as X ³ and X ^3'in the above equation (2), respectively.
Y represents a carbon atom, a silicon atom or a germanium atom.
Each of R ¹¹ and R ²¹ independently has a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a frill group or a substituent which may have a substituent. Indicates a thienyl group which may be present. At least one of R ¹¹ and R ²¹ is either a frill group which may have a substituent or a thienyl group which may have a substituent.
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ , respectively. Independently, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a halogen substituted alkyl group having 1 to 6 carbon atoms, and a trialkyl group. An alkyl group having 1 to 6 carbon atoms having a silyl group, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, a halogen-substituted aryl group having 6 to 18 carbon atoms or a substituent. A heterocyclic group constituting a 5-membered ring or a 6-membered ring which may be possessed is shown. Adjacent groups of R ¹² to R ¹⁹ and R ²² to R ²⁹ may be bonded to each other to form a 6 to 7-membered ring, or the 6 to 7-membered ring may contain an unsaturated bond.
Each of R ³¹ and R ³² independently has a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a halogen-substituted alkyl group having 1 to 6 carbon atoms, and a trialkylsilyl group. It has an alkyl group having 1 to 6 carbon atoms, a silyl group having a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a halogen-substituted aryl group or a substituent having 6 to 18 carbon atoms. It shows a heterocyclic group constituting a good 5-membered ring or 6-membered ring. R ³¹ and R ³² may form a 4- to 7-membered ring together with Y, and if at least one of R ³¹ and R ³² has a cyclic structure, it is composed of R ³¹ and R ³² and Y 4 The 7-membered ring may form a fused ring that shares a part of the constituent atoms of the cyclic structure of R ³¹ and R ³² . ] A catalyst for olefin polymerization, which comprises the following components (I), component (II), component (III) and component (IV).
[Component (I)]
Transition metal compound represented by the following formula (1)

[During the ceremony,
M ¹ represents a transition metal of Group 4 of the periodic table.
L ¹ and L ² represent a ligand containing a cyclopentadienyl structure and are coordinated to M ¹ .
Each of X ¹ and X ² independently has a hydrogen atom, a halogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon containing an oxygen atom or a nitrogen atom. A hydrocarbon group having a number of 3 to 20 or a hydrocarbon group substituted amino group having a carbon number of 1 to 20 is shown.
J ¹ and J ² represent carbon atoms.
A ¹ and A ² indicate a cross-linking group that binds J ¹ and L ¹ and J ² and L ² , respectively, and are selected from the following groups.
-CR ³ _2- , -SiR ³ _2- , -NR ^3- , -PR ^3- , -O-, -S-, [Here, R ³ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Two ^R3s may combine to form a cyclic structure],
R ¹ and R ² independently have a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a hydrocarbon having 1 to 20 carbon atoms including 1 to 6 silicon atoms. A hydrogen group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms is shown. R ¹ and R ² may combine with each other to form a cyclic structure with J ¹ and J ² . ]
[Ingredient (II)]
Transition metal compound selected from the compound group represented by the following formula (2), (3) or (4) Formula (2):
A ³ _q L ³ L 3'M ³ X ³ X ^{3 '}
[During the ceremony,
M ³ indicates a transition metal of Group 4 of the periodic table.
L ³ and L ^{3'independently} represent ligands containing a cyclopentadienyl structure and are coordinated to M ³ . The ligand containing the cyclopentadienyl structure has a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms containing 1 to 6 silicon atoms. Substituted with a hydrocarbon group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group substituted silyl group having 1 to 20 carbon atoms. It may have been. If adjacent substituents are present on L ³ or L ^3' , they may be combined to form a ring structure.
X ³ and X ^3'contain a hydrogen atom ^, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom independently of each other. A hydrocarbon group having 3 to 20 carbon atoms or a hydrocarbon group substituted amino group having 1 to 20 carbon atoms is shown.
A ³ indicates a cross-linking group that crosslinks L ³ and L ^3' , and may or may not be present, and if present, has a cross-linking structure between L ³ and L ^3' .
q is 0 or ¹ and indicates the number of A3. ]
Equation (3):
A ⁴ L ⁴ M ⁴ X ⁴ X ^4'
[During the ceremony,
M ⁴ indicates a transition metal of Group 4 of the periodic table.
L ⁴ represents a ligand containing a cyclopentadienyl structure and is coordinated to M ⁴ . The ligand containing the cyclopentadienyl structure has a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms containing 1 to 6 silicon atoms. Substituted with a hydrocarbon group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group substituted silyl group having 1 to 20 carbon atoms. It may have been.
^X4 and ^{X4'independently} form a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom, which are bonded to the metal ^M4 , respectively. A hydrocarbon group having 3 to 20 carbon atoms or a hydrocarbon group substituted amino group having 1 to 20 carbon atoms is shown.
A ⁴ represents an organic group having a hetero atom bonded to L ⁴ , and is bonded to M ⁴ via the hetero atom. ]
Equation (4):
L ⁵ _m M ⁵ X ⁵ _p
[During the ceremony,
M ⁵ indicates a transition metal of Group 3 to 11 of the Periodic Table.
The m ^L5s each independently represent a hydrocarbon group substituted with a substituent having an atom selected from two or more oxygen, nitrogen, phosphorus, and sulfur atoms, and at least two of the oxygen. , Nitrogen, phosphorus, and an atom selected from sulfur atoms are bonded to ^M5 .
Each of the p X ^5s independently has a hydrogen atom, a halogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon containing an oxygen atom or a nitrogen atom. The number 3 to 20 hydrocarbon groups or neutral Lewis bases are shown.
m represents the number of L5 and is ¹ or 2.
p indicates the number of X, which is a number selected so that the transition metal compound of the formula (4) is electrically neutral. ]
[Ingredient (III)]
A compound that reacts with a transition metal compound of component (I) and component (II) to form a cationic compound [component (IV)].
Fine particle carrier A catalyst for olefin polymerization produced by mixing the following components (I), component (II), component (III) and component (IV).
[Component (I)]
Transition metal compound represented by the following formula (1)

[During the ceremony,
M ¹ represents a transition metal of Group 4 of the periodic table.
L ¹ and L ² represent a ligand containing a cyclopentadienyl structure and are coordinated to M ¹ .
Each of X ¹ and X ² independently has a hydrogen atom, a halogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon containing an oxygen atom or a nitrogen atom. A hydrocarbon group having a number of 3 to 20 or a hydrocarbon group substituted amino group having a carbon number of 1 to 20 is shown.
J ¹ and J ² represent carbon atoms.
A ¹ and A ² indicate a cross-linking group that binds J ¹ and L ¹ and J ² and L ² , respectively, and are selected from the following groups.
-CR ³ _2- , -SiR ³ _2- , -NR ^3- , -PR ^3- , -O-, -S-, [Here, R ³ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Two ^R3s may combine to form a cyclic structure],
R ¹ and R ² are independent hydrocarbons having 1 to 20 carbon atoms including a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 1 to 6 silicon atoms. A hydrogen group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms is shown. R ¹ and R ² may combine with each other to form a cyclic structure with J ¹ and J ² . ]
[Ingredient (II)]
Transition metal compound selected from the compound group represented by the following formula (2), (3) or (4) Formula (2):
A ³ _q L ³ L 3'M ³ X ³ X ^{3 '}
[During the ceremony,
M ³ indicates a transition metal of Group 4 of the periodic table.
L ³ and L ^{3'independently} represent ligands containing a cyclopentadienyl structure and are coordinated to M ³ . The ligand containing the cyclopentadienyl structure has a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms containing 1 to 6 silicon atoms. Substituted with a hydrocarbon group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group substituted silyl group having 1 to 20 carbon atoms. It may have been. If adjacent substituents are present on L ³ or L ^3' , they may be combined to form a ring structure.
X ³ and X ^3'contain a hydrogen atom ^, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom independently of each other. A hydrocarbon group having 3 to 20 carbon atoms or a hydrocarbon group substituted amino group having 1 to 20 carbon atoms is shown.
A ³ indicates a cross-linking group that crosslinks L ³ and L ^3' , and may or may not be present, and if present, has a cross-linking structure between L ³ and L ^3' .
q is 0 or ¹ and indicates the number of A3. ]
Equation (3):
A ⁴ L ⁴ M ⁴ X ⁴ X ^4'
[During the ceremony,
M ⁴ indicates a transition metal of Group 4 of the periodic table.
L ⁴ represents a ligand containing a cyclopentadienyl structure and is coordinated to M ⁴ . The ligand containing the cyclopentadienyl structure has a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms containing 1 to 6 silicon atoms. Substituted with a hydrocarbon group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms including an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group substituted silyl group having 1 to 20 carbon atoms. It may have been.
^X4 and ^{X4'independently} form a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an oxygen atom or a nitrogen atom, which are bonded to the metal ^M4 , respectively. A hydrocarbon group having 3 to 20 carbon atoms or a hydrocarbon group substituted amino group having 1 to 20 carbon atoms is shown.
A ⁴ represents an organic group having a hetero atom bonded to L ⁴ , and is bonded to M ⁴ via the hetero atom. ]
Equation (4):
L ⁵ _m M ⁵ X ⁵ _p
[During the ceremony,
M ⁵ indicates a transition metal of Group 3 to 11 of the Periodic Table.
The m ^L5s each independently represent a hydrocarbon group substituted with a substituent having an atom selected from two or more oxygen, nitrogen, phosphorus, and sulfur atoms, and at least two of the oxygen. , Nitrogen, phosphorus, and an atom selected from sulfur atoms are bonded to ^M5 .
Each of the p ^X5s has a hydrogen atom, a halogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon containing an oxygen atom or a nitrogen atom, which independently bond with M5. The number 3 to 20 hydrocarbon groups or neutral Lewis bases are shown.
m represents the number of L5 and is ¹ or 2.
p indicates the number of X, which is the number selected so that the transition metal compound of the formula (4) is electrically neutral. ]
[Ingredient (III)]
A compound that reacts with a transition metal compound of component (I) and component (II) to form a cationic compound [component (IV)].
Fine particle carrier A method for producing an ethylene-based polymer, which comprises copolymerizing an α-olefin selected from the group consisting of ethylene and an α-olefin other than ethylene by using the olefin polymerization catalyst according to claim 9 or 10.

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