Catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer

Abstract

To provide an olefin polymerization catalyst component that can 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.SOLUTION: Provided is an olefin polymerization catalyst component in which, as a component (I), a transition metal compound (metallocene complex) having a particular metallocene bridge structure and a low comonomer copolymerization ability, and, as a component (II), a particular transition metal compound having a high comonomer copolymerization ability are combined.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an olefin polymerization catalyst component useful for producing olefin polymers and copolymers, an olefin polymerization catalyst containing the catalyst component, and a method for producing an ethylene homopolymer or an ethylene / α-olefin copolymer using the olefin polymerization catalyst. [Background technology]

[0002] Olefin polymers such as polyethylene and polypropylene are widely used as plastic molding materials. Olefin polymers as molding materials are required to have moldability, such as fluidity, melt tension, and elongational viscosity in the molten state, as well as physical properties, such as hardness, rigidity, impact strength, heat resistance, durability, and transparency after molding, suitable for the intended use of the molded article. In this context, polyolefins produced using metallocene catalysts for olefin polymerization have been increasingly used in recent years because they have high uniformity in polymer molecular structure, such as molecular weight distribution and copolymer composition distribution, and are excellent in various mechanical properties, such as impact strength and long life. However, although metallocene-based polyolefins are excellent in various mechanical properties, due to their narrow molecular weight distribution, they are inferior in properties important for polyolefin molding processing, such as melt tension and melt fluidity, and do not satisfy sufficient performance in terms of molding processing.

[0003] It is known to use a catalyst system that combines two types of metallocene catalysts in order to improve the moldability and physical properties of olefin polymers after molding. For example, Patent Document 1 discloses a method for producing polyolefins having a wide molecular weight distribution and a high molecular weight, which uses a mixture of two metallocenes selected from a specific group of metallocene compounds.

[0004] In addition, attempts have been made to obtain ethylene / α-olefin copolymers with adjusted molecular weight distribution and the amount of branched chains derived from α-olefin (i.e., the amount of comonomer introduced) by copolymerizing ethylene and the comonomer α-olefin using a catalyst system that combines two types of metallocene catalysts with different comonomer copolymerization abilities. For example, Patent Documents 2 to 4 disclose that copolymerization of ethylene and a comonomer using a catalyst system combining a metallocene having low comonomer copolymerization ability with a metallocene having high comonomer copolymerization ability has resulted in an ethylene / α-olefin copolymer having a broad multimodal molecular weight distribution and containing many comonomer-derived branched chains in the high molecular weight region of the molecular weight distribution, compared to ethylene / α-olefin copolymers produced using only one type of metallocene catalyst.

[0005] Patent Document 2 describes copolymerization of ethylene and a comonomer by using a combination of a catalyst compound incorporating a small amount of comonomer and a catalyst compound incorporating a large amount of comonomer, but the former catalyst compound incorporating a small amount of comonomer is a metallocene having a relatively low ability to copolymerize comonomer, and the latter catalyst compound incorporating a large amount of comonomer is a metallocene having a relatively high ability to copolymerize comonomer. Patent Document 3 describes the copolymerization of ethylene and a comonomer by using a combination of a specific first metallocene compound and a specific second metallocene compound. 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 the copolymerization of ethylene and a comonomer by using a combination of two different components (A) and (B) selected from the group of metallocene compounds of Group 4 of the periodic table. However, according to the description in paragraph 0020 of Patent Document 4, the former component (A) is a metallocene having a relatively low ability to copolymerize a comonomer, and the latter component (B) is a metallocene having a relatively high ability to copolymerize a comonomer.

[0006] Furthermore, Non-Patent Document 1 describes an experiment in which ethylene and propylene homopolymers were synthesized using dichloro{o-phenylenedimethylenebis(η5-1-indenyl)zirconium}, which is one of the bridged metallocenes. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 7-179512 [Patent Document 2] Patent Publication No. 2007-284691 [Patent Document 3] Special table number 2009-504901 [Patent Document 4] Patent Publication No. 2010-202791 [Non-patent literature]

[0008] [Non-Patent Document 1] Macromolecules, 1995, vol.28, p.4801 Summary of the Invention [Problem to be solved by the invention]

[0009] In the technology of controlling the molecular weight distribution and comonomer composition distribution using a plurality of transition metal compounds, in order to produce an olefin polymer having excellent moldability and a good balance between rigidity, strength, and durability, an olefin polymerization catalyst is required that can broaden the molecular weight distribution and selectively introduce a comonomer into the high molecular weight side of the molecular weight distribution, thereby increasing the amount of comonomer introduced into the high molecular weight side. However, as will be described later, the metallocene catalysts disclosed in Patent Documents 2 to 4 do not necessarily fully satisfy the above-mentioned technical requirements. Furthermore, Non-Patent Document 1 does not describe anything about the copolymerization ability of dichloro{o-phenylenedimethylenebis(η5-1-indenyl)zirconium} in copolymerizing ethylene and an α-olefin.

[0010] In contrast to the above-mentioned conventional techniques, an object of the present invention is to provide a catalyst component for olefin polymerization that can produce an olefin polymer having a sufficiently broad 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. Another object of the present invention is to provide a process for producing an ethylene polymer having excellent moldability and a good balance between rigidity, strength and durability, by using the above-mentioned catalyst component for olefin polymerization. [Means for solving the problem]

[0011] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that by using a catalyst containing a catalyst component combining a transition metal compound (metallocene complex) having a specific metallocene crosslink structure and low comonomer copolymerization ability with a specific transition metal compound having high comonomer copolymerization ability, it is possible to obtain an olefin polymer having a sufficiently broad molecular weight distribution, with the distribution spreading 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, and have completed the present invention.

[0012] That is, the catalyst component for olefin polymerization of the present invention is a catalyst component characterized by containing the following component (I) and component (II): [Component (I)] A transition metal compound represented by the following formula (1):

[0013] [ka]

[0014] [In the formula, M 1 indicates a transition metal in Group 4 of the periodic table. L 1 and L2 indicates a ligand containing a cyclopentadienyl structure, and M 1 It is coordinated to. X 1 and X 2 are each independently, M 1 and represents 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, which is bonded to the J 1 and J 2 indicates a carbon atom. A 1 and A 2 are J 1 and L 1 , J 2 and L 2 and is selected from the following group: -CR 3 2-, -SiR 3 2-, -NR 3 -,-PR 3 -, -O-, -S-, [where R 3 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and two R 3 may be linked to form a cyclic structure], R 1 and R 2 R each independently represents a hydrogen 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 and containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms. 1 and R 2 When they combine, J 1 and J. 2 may form a cyclic structure together with

[0015] [Component (II)] The following formula (2) is expressed as transition metal compounds A 3 q L3 L 3’ M 3 X 3 X 3’ Formula (2) [In the formula, M 3 indicates a transition metal in Group 4 of the periodic table. L 3 and L 3’ each independently represents a ligand containing a cyclopentadienyl structure, M 3 The ligand containing a cyclopentadienyl structure may be substituted with 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 and containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms. 3 or L 3’ When adjacent substituents are present on the aryl group, they may be bonded to form a ring structure. X 3 and X 3’ are each independently, M 3 and represents 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, which is bonded to the A 3 L 3 and L 3’ represents a bridging group bridging an alkylene group having 1 to 20 carbon atoms which may have a substituent, a silylene group which may have a substituent, or a germylene group which may have a substituent, May or may not be present, and if present, L 3 and L 3’ There is a bridge structure between them. q is 0 or 1, and A 3 Indicates the number of

[0018] The olefin polymerization catalyst of the present invention is an olefin polymerization catalyst characterized by containing the following components (I), (II), (III), and (IV), and an olefin polymerization catalyst produced by mixing the following components (I), (II), (III), and (IV). [Component (I)] A transition metal compound represented by the above formula (1) [Component (II)] A transition metal compound represented by the above formula (2) [Component (III)] A compound that reacts with the transition metal compounds of component (I) and component (II) to generate a cationic compound. [Component (IV)] Microparticle carrier

[0019] Furthermore, the method for producing an ethylene polymer of the present invention is characterized in that it comprises copolymerizing ethylene and an α-olefin selected from the group consisting of α-olefins other than ethylene using the olefin polymerization catalyst of the present invention. [Effects of the Invention]

[0020] According to the present invention, it is possible to provide a catalyst component for olefin polymerization that can produce an olefin polymer having a sufficiently broad 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. It is also possible to provide an olefin polymerization catalyst containing this catalyst component, and a process for producing an olefin polymer, particularly an ethylene polymer, using this catalyst. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 shows the results of GPC-IR of the polyethylene obtained in Example 1. [Figure 2] FIG. 2 shows the results of GPC-IR of the polyethylene obtained in Example 4. [Figure 3] FIG. 3 shows the results of GPC-IR of the polyethylene obtained in Example 7. DETAILED DESCRIPTION OF THE INVENTION

[0022] The present invention will be described below. In the present invention, "polymerization" collectively refers to homopolymerization of one type of monomer and copolymerization of multiple types of monomers, and when there is no particular need to distinguish between the two, they will be collectively referred to simply as "polymerization." In the present invention, the use of "to" indicating a range of values ​​means that the values ​​before and after it are included as the lower limit and upper limit. In the present invention, "Ph" represents phenyl, "Me" represents methyl or a methyl group, "Et" represents ethyl or an ethyl group, "Pr" represents propyl or a propyl group, and "Hex" represents hexyl or a hexyl group. Furthermore, the "i" attached to the alkyl group name represents an isomeric structure, "n" represents normal, "t" represents tertiary, and "c" represents cyclo. Note that when an alkyl group does not have an isomeric structure attached to it, it indicates a normal structure.

[0023] I. Catalyst Components for Olefin Polymerization The catalyst component for olefin polymerization of the present invention is characterized by comprising component (I), which is a transition metal compound represented by formula (1) described below, and component (II), which is a transition metal compound selected from the group of compounds represented by formula (2), formula (3), or formula (4) described below. Comparing component (I) and component (II), component (I) is a transition metal compound with relatively low copolymerizability, while component (II) is a transition metal compound with relatively high copolymerizability, and both transition metal compounds have catalytic activity for olefin polymerization. The olefin polymerization catalyst component of the present invention is useful as a catalytically active component of an olefin polymerization catalyst capable of producing an olefin polymer having a sufficiently broad 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. The olefin polymerization catalyst component of the present invention can be combined with a cocatalyst and a carrier to produce an olefin polymerization catalyst.

[0024] In the technology of controlling the molecular weight distribution and comonomer composition distribution using a plurality of transition metal compounds, in order to produce an olefin polymer having excellent moldability and a good balance between rigidity, strength, and durability, an olefin polymerization catalyst is required that can broaden the molecular weight distribution and selectively introduce a comonomer into the high molecular weight side of the molecular weight distribution, thereby increasing the amount of comonomer introduced into the high molecular weight side.

[0025] Table 1 and paragraphs 0035 to 0036 of Patent Document 2 show the relationships between the hexene / ethylene ratio and the density, melt index (MI) and MFR for several ethylene-hexene copolymers obtained by copolymerizing ethylene and hexene comonomers in a gas phase process using a catalyst compound that incorporates a small amount of comonomer (i.e., a metallocene with low comonomer copolymerization ability) or a catalyst compound that incorporates a large amount of comonomer (i.e., a metallocene with high comonomer copolymerization ability) alone, while changing the hexene / ethylene ratio (C6 / C2) and keeping other conditions the same. Generally, when olefins are copolymerized using a metallocene with low comonomer copolymerization ability, the comonomer cannot be sufficiently introduced unless the comonomer / monomer ratio of the charged monomers is high. On the other hand, when olefins are copolymerized using a metallocene with high comonomer copolymerization ability, the comonomer can be sufficiently introduced even if the comonomer / monomer ratio of the charged monomers is low. If a metallocene with low comonomer copolymerization ability and a metallocene with high comonomer copolymerization ability are used alone and copolymerized under the same polymerization conditions except for the comonomer / monomer ratio of the charged monomers, in order to obtain copolymers with the same density, the lower the comonomer copolymerization ability of the metallocene, the higher the comonomer / monomer ratio of the charged monomers must be. In other words, when comparing copolymers obtained using two different metallocenes with the same density, i.e., in terms of density, the copolymer with a higher hexene / ethylene ratio in the monomer feed during polymerization has a lower comonomer copolymerization ability of the metallocene used, and conversely, the copolymer with a lower hexene / ethylene ratio in the monomer feed during polymerization has a higher comonomer copolymerization ability of the metallocene used.

[0026] Paragraph 0036 of Patent Document 2 states that the molar ratio of comonomer / monomer required by a catalyst incorporating a small amount of comonomer to produce a polymer with a density of 0.920 g / cc is preferably at least twice, more preferably three times, even more preferably four times, and even more preferably five times the molar ratio of comonomer / monomer required by a catalyst incorporating a large amount of comonomer to produce a polymer with a density of 0.920 g / cc. According to the data shown in Table 1 of Patent Document 2, when the hexene / ethylene ratio of the monomer feed of a copolymer obtained using a catalyst with a small amount of comonomer incorporation is compared in terms of density, the ratio between the highest hexene / ethylene ratio among examples using a catalyst with a small amount of comonomer incorporation and the lowest hexene / ethylene ratio among examples using a catalyst with a large amount of comonomer incorporation is about 10 times (for example, comparing the example of the Meso-O(MeSiIND) complex with a C / C molar ratio of 0.056 and a density of 0.934 listed on line 8 of Table 1 of Patent Document 2 with the example of the MeSi(HIND) complex with a C / C molar ratio of 0.005 and a density of 0.929 listed on line 35 of the same table). However, no experiments were reported in which copolymerizations were actually performed using a combination of a catalyst with a small amount of comonomer incorporation and a catalyst with a large amount of comonomer incorporation, such that the ratio in copolymerization ability was about 10 times. Furthermore, Example 5C of Patent Document 2 describes that the molecular weight distribution (Mw / Mn) of an ethylene-hexene copolymer obtained by using a combination of a catalyst incorporating a small amount of comonomer and a catalyst incorporating a large amount of comonomer was approximately 3.5 to 4.5, which cannot be said to be a sufficiently wide molecular weight distribution from the viewpoint of moldability.

[0027] Patent Document 3 does not clearly describe the difference in copolymerization ability when the first metallocene compound (i.e., a metallocene having a high comonomer copolymerization ability) is used alone and the copolymerization ability when the second metallocene compound (i.e., a metallocene having a low comonomer copolymerization ability) is used alone, i.e., the reactivity ratio. However, referring to the GPC-IR data shown in Figure 2 of Patent Document 3, it is estimated that the ratio of the number of short chain branches in the polymer at the low molecular weight peak obtained by using the second metallocene compound alone to the number of short chain branches in the polymer at the high molecular weight peak obtained by using the first metallocene compound alone is about three times.

[0028] Table 5 of Patent Document 4 shows the number of short chain branches (1 / 1000C, the number of short chain branches per 1000 carbon atoms) when components (A-1) to (A-5) (i.e., metallocenes with relatively low comonomer copolymerization ability) are used alone, and the number of short chain branches (1 / 1000C) when components (B-1) to (B-2) (i.e., metallocenes with relatively high comonomer copolymerization ability) are used alone. The difference, i.e., the ratio, between the smallest number of short chain branches in the low-molecular-weight components obtained by using components (A-1) to (A-5) alone and the largest number of short-chain branches in the high-molecular-weight components obtained by using components (B-1) to (B-2) alone is about 5.5 times.

[0029] In contrast to the above-described conventional techniques, the present invention uses an olefin polymerization catalyst containing a catalyst component combining the above-described component (I) as a transition metal compound with low copolymerizability and the above-described component (II) as a transition metal compound with high copolymerizability to copolymerize an olefin main monomer and an olefin comonomer. This polymerization reaction synthesizes a copolymer with a low molecular weight and a low comonomer content through the catalytic reaction mediated by component (I) in a single reaction system, while simultaneously synthesizing a copolymer with a high molecular weight and a high comonomer content through the catalytic reaction mediated by component (II). As a result, an olefin polymer is obtained in which the copolymer with a low comonomer content produced by the catalytic reaction mediated by component (I) is predominant in the low molecular weight range, while the copolymer with a high comonomer content produced by the catalytic reaction mediated by component (II) is predominant in the high molecular weight range. Therefore, when the reaction system as a whole is considered, it is possible to produce an olefin polymer having a sufficiently broad 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. In particular, the catalyst component combining the above component (I) and component (II) has the advantage of being able to increase the difference between the comonomer content on the low molecular weight side and the comonomer content on the high molecular weight side more than conventional catalysts.

[0030] The reason why component (I) produces polymers with low comonomer content is that the two ligands (L 1 , L 2 ) is a bridging group (A 1 , A 2 ) to form a specific chemical structure (-L 1 -A 1 -J 1 =J 2 -A 2 -L 2 -), these two ligands (L 1 , L 2 ) is the central metal (M 1), the substituents on the ligand take a structure that protrudes in the direction of the monomer coordination. However, when the ligand is indenyl, it is thought that the fused ring part with 4 carbon atoms fused to the 5-membered ring takes a structure that protrudes in the direction of the monomer coordination. 1 -A 1 -J 1 =J 2 -A 2 -L 2 -) in J 1 =J 2 takes an SP2 hybrid orbital, and the bridging group (A 1 , A 2 ) are connected by sp3 hybrid orbitals, the right angle and distance are established, making the protrusion shown above possible. When there is an obstacle in the direction of the monomer coordination, it becomes difficult for larger comonomers to coordinate, so monomers such as ethylene coordinate to the central metal and turn into polymers, but comonomers such as 1-hexene are difficult to incorporate into the polymer. To make it easier to adopt the above structure, the ligand (L 1 , L 2 When A ) is indenyl, a bridging group (A ) is at the 1- or 3-position of the indenyl. 1 , A 2 ) is preferably bonded to the

[0031] As described above, by combining component (I), a metallocene with low copolymerizability and a specific bond distance and angle due to the bridging moiety, with component (II), a transition metal compound with high copolymerizability, it is possible to increase the difference between the comonomer content in the low molecular weight side and the high molecular weight side of the copolymer. As component (II), a high molecular weight transition metal compound with copolymerizability is used, preferably a bridged bisindene type, a bridged cyclopentadiene-fluorene type, or a bridged bisfluorene type. In this case, the bridge group is preferably silicon or carbon atom. It is believed that the bridge group widens the dihedral angle of the two faces formed by the five-membered ring moieties of the two ligands, eliminating obstacles to coordinating the comonomer and increasing reactivity with the comonomer. A variety of ligand combinations are possible, but among the ligands containing a cyclopentadienyl structure, bisindene, cyclopentadiene-fluorene, and bisfluorene types are preferred as they have a high molecular weight.

[0032] 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 an olefin polymer and the correlation curve of the molecular weight of a polymer contained in the olefin polymer and the number of branches derived from a comonomer are superimposed on one graph with the molecular weight on a common axis, and the molecular weight distribution curve is divided into a low molecular weight region and a high molecular weight region based on the shape of the molecular weight distribution curve, and the number of branches present in the low molecular weight region and the number of branches present in the high molecular weight region are compared. In this method, the number of branches at the low molecular weight peak of the molecular weight distribution curve may be compared with the number of branches at the high molecular weight peak of the molecular weight distribution curve. Method 2: The molecular weight distribution curve of the olefin polymer and the cumulative curve of the number of branches derived from the comonomer, obtained from 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 one graph, with the molecular weight as the common axis, and the low molecular weight region and the high molecular weight region are separated from the shape of the molecular weight distribution curve, and the slope (rapidity) of the cumulative number of branches from the low molecular weight region to the high molecular weight region is observed. Method 3: A polymerization catalyst containing component (I) but not containing component (II), and a polymerization catalyst containing component (II) but not containing component (I), are each used alone to copolymerize olefins under the same polymerization conditions, thereby producing a low-molecular-weight copolymer from component (I), which is a transition metal compound with low copolymerizability, and a high-molecular-weight copolymer from component (I), which is a transition metal compound with high copolymerizability, and the number of branches contained in the low-molecular-weight copolymer and the number of branches contained in the high-molecular-weight copolymer are compared.

[0033] Although this is merely an example of the present invention, according to the present invention, the molecular weight distribution (Mw / Mn) of the olefin polymer can be set to a range of 6 to 60, and at the same time, the ratio of the comonomer content on the high molecular weight side to the comonomer content on the low molecular weight side determined by the above method 3 (comonomer content on the high molecular weight side / comonomer content on the low molecular weight side) can be set to 4 times or more, further 8 times or more, and further 10 times or more.

[0034] Components (I) and (II) will be described below. In this specification, the term "a hydrocarbon group having a to b carbon atoms and containing a heteroatom X such as an oxygen atom, sulfur atom, nitrogen atom or silicon atom" may be used in some cases, such as "a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, sulfur atom or nitrogen atom" or "a hydrocarbon group having 1 to 20 carbon atoms and containing 1 to 6 silicon atoms." In this case, the term "hydrocarbon group containing a hetero atom X" means that a hetero atom X that is not bonded to a hydrogen atom or that is bonded only to a carbon atom is present on or within the carbon chain of the hydrocarbon group. For example, examples of cases in which a heteroatom having only bonds to carbon atoms is present on the carbon chain of a hydrocarbon group include cases in which an alkoxy group, a thioether group, a dialkylamino group, or a trialkylsilyl group is bonded to the terminal of an alkyl group, bonded in a pendant form to the middle of an alkyl group, or an oxo group is bonded to the terminal or middle of an alkyl group. Furthermore, "existing within the carbon chain of a hydrocarbon group" means that the carbon chain of the hydrocarbon group is interrupted by a heteroatom. For example, when it is present within the carbon chain of a hydrocarbon group, an ether bond or a thioether bond is inserted in the middle of the chain hydrocarbon group, or a cyclic ether structure is formed. In this case, the carbon number of the hydrocarbon group containing heteroatoms refers to the number of carbon atoms contained in the entire hydrocarbon group containing heteroatoms. For example, a "hydrocarbon group containing heteroatoms and having a to b carbon atoms" means that the total number of carbon atoms in the hydrocarbon group, including the carbon atoms in the carbon chain separated by heteroatoms, is a to b. More specifically, the carbon number of a methoxymethyl group (CHO-CH-) is 2.

[0035] 1. Component (I) The component (I) used in the present invention is a transition metal compound represented by the following formula (1).

[0036] [ka]

[0037] [In the formula, M 1 indicates a transition metal in Group 4 of the periodic table. L 1 and L 2 indicates a ligand containing a cyclopentadienyl structure, and M 1 It is coordinated to. X 1 and X 2 are each independently, M 1and represents 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, which is bonded to the J 1 and J 2 indicates a carbon atom. A 1 and A 2 are J 1 and L 1 , J 2 and L 2 and is selected from the following group: -CR 3 2-, -SiR 3 2-, -NR 3 -,-PR 3 -, -O-, -S-, [where R 3 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and two R 3 may be linked to form a cyclic structure], R 1 and R 2 R each independently represents a hydrogen 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 and containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms. 1 and R 2 When they combine, J 1 and J. 2 may form a cyclic structure together with

[0038] M 1 is a transition element in group 4 of the periodic table. 1 As the cation, for example, a titanium atom (Ti), a zirconium atom (Zr), or a hafnium atom (Hf) is used, but a zirconium atom is preferred because a zirconium atom can lower the copolymerization ability and increase the polymerization activity compared to a hafnium atom.

[0039] L 1 and L2 contains a cyclopentadienyl structure, and M 1 The ligand containing a cyclopentadienyl structure is a ligand that coordinates to L. Examples of the ligand containing a cyclopentadienyl structure include a ligand having a cyclopentadinyl skeleton, a ligand having an indenyl skeleton, and a ligand having a fluorenyl skeleton. The ligand containing a cyclopentadienyl structure may have a part of the unsaturated bond contained in the skeleton substituted with a hydrogen atom, and for example, a ligand having an indenyl skeleton may be a tetrahydroindenyl group. In addition, L 1 and L 2 may be different from each other, such as a cyclopentadienyl skeleton and an indenyl skeleton, a cyclopentadienyl skeleton and a fluorenyl skeleton, or an indenyl skeleton and a fluorenyl skeleton. The ligand containing a cyclopentadienyl structure may have a substituent. In particular, in the case of a ligand having a cyclopentadienyl skeleton, it is preferable that the number of substitutions is two 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 and containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom, and a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms. L 1 or L 2 When adjacent substituents are present on the ring, they may be bonded to form a ring structure. 1 or L 2 The positions of the above substituents are arbitrarily selected, and in the case of an indenyl skeleton, examples include mono-substitution at the 2-, 3-, and 4-positions, and di-substitution at the 4-, 7-, or 5-, 6-positions.

[0040] 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 alkyl groups or cycloalkyl groups such as 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, a t-butyl group, an n-pentyl group, a neopentyl group, an n-hexyl group, an octyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group; alkenyl groups such as a vinyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group; and alkenyl groups having an alicyclic substituent such as a cyclopentylmethyl group or a 2-cyclohexylethyl group. alkyl groups; monocyclic or condensed ring aryl groups which may be substituted with a saturated or unsaturated hydrocarbon group, such as a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a 4-t-butylphenyl group, a 3,5-di-t-butylphenyl group, a 4-vinylphenyl group, a 3-allylphenyl group, a 4-(3-butenyl)phenyl group, or a naphthyl group; and alkyl groups having an aromatic substituent, such as a benzyl group or a 2-phenylethyl group.

[0041] 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, and a phenoxy group. Specific examples of hydrocarbon groups having 1 to 20 carbon atoms and containing 1 to 6 silicon atoms include hydrocarbon groups substituted with 1 to 6 trialkylsilyl groups, where the total number of carbon atoms, including the carbon atoms of the alkylsilyl groups, is 1 to 20. More specific examples include alkylsilyl-substituted alkyl groups such as a bis(trimethylsilyl)methyl group, a bis(t-butyldimethylsilyl)methyl group, a trimethylsilylethyl group, a triethylsilylethyl group, and a 2-trimethylsilylpropyl group; and alkylsilyl-substituted aromatic hydrocarbon groups such as a 4-trimethylsilylphenyl group.

[0042] Specific examples of the halogen-substituted hydrocarbon group having 1 to 20 carbon atoms include halogenated alkyl groups such as bromomethyl, chloromethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 4-chlorobutyl, 3-fluorobutyl, and 4,4,4-trifluorobutyl; halogenated cycloalkyl groups such as 2-bromocyclopentyl, 2,3-dibromocyclopentyl, 2-bromo-3-iodocyclopentyl, 2,3-dibromocyclohexyl, and 2-chloro-3-iodocyclohexyl; halogenated aromatic groups such as 2-chlorophenyl, 4-chlorophenyl, 3,5-dichlorophenyl, and 2,3,4,5,6-pentafluorophenyl; and halogenated alkyl aromatic groups such as 4-trifluoromethylphenyl.

[0043] Specific examples of hydrocarbon groups having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom or a nitrogen atom include the following: those containing oxygen include alkoxyalkyl groups such as ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, t-butoxymethyl group, methoxyethyl group, ethoxyethyl group, 4-methoxybutyl group, 3-ethoxybutyl group and 6-methoxyhexyl group; alkoxy aromatic groups such as 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group and 2,4-dimethoxyphenyl group; acetyl group, 1-oxopropyl group, 1-oxo-n-butyl group, 2-methyl-1-oxopropyl group; oxo-containing hydrocarbon groups such as 2-dimethyl-1-oxopropyl, phenylacetyl, diphenylacetyl, and benzoyl groups; cyclic ether groups such as 2-furyl, 2-tetrahydrofuryl, and 2-methylfuryl groups; sulfur-containing groups such as 2-thienyl, 2-tetrahydrothienyl, and 2-methylthienyl groups; and nitrogen-containing groups such as dimethylaminomethyl, diethylaminomethyl, di-i-propylaminomethyl, bis(dimethylamino)methyl, bis(di-i-propylamino)methyl, (dimethylamino)(phenyl)methyl, aminoethyl, dimethylaminoethyl, diethylaminoethyl, 1-(methylimino)ethyl, 1-(phenylimino)ethyl, 1-[(phenylmethyl)imino]ethyl, and dimethylaminohexyl groups; and amino-substituted aromatic groups such as 4-aminophenyl and 4-dimethylaminophenyl groups.

[0044] Specific examples of the hydrocarbon-substituted silyl group having 1 to 20 carbon atoms include alkylsilyl groups such as trimethylsilyl group, tri-t-butylsilyl group, di-t-butylmethylsilyl group, and t-butyldimethylsilyl group, and aromatic silyl groups such as triphenylsilyl group, diphenylmethylsilyl group, and phenyldimethylsilyl group.

[0045] X 1 and X 2 are each independently, M 1is 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, which is bonded to Specific examples of halogen atoms include the above L 1 and L 2 Specific examples of halogen atoms explained for the substituents of X 1 and X 2 The following can also be mentioned. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include the above L 1 and L 2 Specific examples of the hydrocarbon group having 1 to 20 carbon atoms described for the substituent of X 1 and X 2 The following can also be mentioned. Specific examples of the alkoxy group having 1 to 20 carbon atoms include the above L 1 and L 2 Specific examples of the alkoxy group having 1 to 20 carbon atoms described for the substituent of X 1 and X 2 The following can also be mentioned. Specific examples of the hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom or a nitrogen atom include the above-mentioned L 1 and L 2 Specific examples of the hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom or a nitrogen atom as described for the substituent of X 1 and X 2 The following can also be mentioned. Specific examples of the hydrocarbon-substituted amino group having 1 to 20 carbon atoms include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a di-i-butylamino group, a di-t-butylamino group, and a diphenylamino group.

[0046] J 1 and J 2 indicates a carbon atom. 1 and J 2 is bonded with a double bond, and J 1 and J 2 becomes an sp2 hybrid orbital, 1 and A2 in collaboration with ligand L 1 and L 2 is a transition metal M 1 The ligand L can be coordinated to the 1 and L 2 is a transition metal M 1 As an atom that can be coordinated to the atom at a moderate angle, J 1 and J 2 The carbon atom is the best position for this.

[0047] A 1 and A 2 are J 1 and L 1 , J 2 and L 2 and a bridging group connecting the two, selected from the group consisting of: -CR 3 2-, -SiR 3 2-, -NR 3 -,-PR 3 -, -O-, -S-, [where R 3 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and two R 3 may be linked to form a ring structure. R 3 Specific examples of the hydrocarbon group having 1 to 10 carbon atoms include L 1 and L 2 Among the specific examples of hydrocarbon groups described for the substituents of the formula (1), those having 1 to 10 carbon atoms are designated as R 3 The following can also be mentioned. A 1 and A 2 As the alkyl group, a methylene group which is unsubstituted or has an alkyl group having 1 to 4 carbon atoms, and a silylene group which is unsubstituted or has an alkyl group having 1 to 4 carbon atoms are preferred.

[0048] R 1 and R 2are each independently a hydrogen 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 and containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms.

[0049] Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include the above L 1 and L 2 Specific examples of the hydrocarbon group having 1 to 20 carbon atoms described for the substituents of R 1 and R 2 The following can also be mentioned. Specific examples of the alkoxy group having 1 to 20 carbon atoms include the above L 1 and L 2 Specific examples of the alkoxy group having 1 to 20 carbon atoms described for the substituent of R 1 and R 2 The following can also be mentioned. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms and containing 1 to 6 silicon atoms include the above-mentioned L 1 and L 2 Specific examples of the hydrocarbon group having 1 to 20 carbon atoms and containing 1 to 6 silicon atoms as described for the substituents of R 1 and R 2 The following can also be mentioned. Specific examples of the halogen-substituted hydrocarbon group having 1 to 20 carbon atoms include the above-mentioned L 1 and L 2 Specific examples of the halogen-substituted hydrocarbon group having 1 to 20 carbon atoms described for the substituents of R 1 and R 2 The following can also be mentioned. Specific examples of the hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom include the above-mentioned L 1 and L 2 Specific examples of the hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom described for the substituent of 1 and R 2 The following can also be mentioned. Specific examples of the hydrocarbon-substituted silyl group having 1 to 20 carbon atoms include the above-mentioned L 1 and L 2 Specific examples of the hydrocarbon-substituted silyl group having 1 to 20 carbon atoms described above for the substituent are shown below as R 1 and R 2 The following can also be mentioned.

[0050] R 1 and R 2 and J 1 and J. 2 When these together form a part of a cyclic structure, examples of the cyclic structure include aromatic rings such as benzene-1,2-diyl group, naphthalene-2,3-diyl group, and phenanthrene-9,10-diyl group; 4- to 7-membered rings composed of carbon atoms such as cyclobutane-1,2-diyl group (cyclobutylidene group), cyclopentane-1,2-diyl group (cyclopentylidene group), and cyclohexane-1,2-diyl group (cyclohexylidene group); and alicyclic bicyclo rings such as bicyclo[2.2.1]heptane-diyl group (norbornane-diyl group) and bicyclo[4.4.0]decane-diyl group (decalin-diyl group). These ring structures have J 1 and J 2 The ring structure may contain a double bond other than the double bond between the rings, or may have a hydrocarbon group such as an alkyl group or an alkenyl group, a halogen atom, or other substituents on the ring structure. In addition, this cyclic structure may have a bridged structure that bridges the atoms that form the ring structure.

[0051] Furthermore, R 1 and R 2 and J 1 and J. 2 When there are two or more substituents on the ring skeleton containing R, the substituents are bonded to each other to close the ring, and R 1 and R 2 and J 1 and J. 2 and may form a condensed polycyclic structure in which some of the constituent atoms of the ring skeleton are shared. R 1 and R 2 and J 1 and J.2 and a fused ring containing another ring skeleton is R 1 and R 2 and J 1 and J. 2 The fused ring may have a substituent on a ring skeleton other than the ring skeleton containing the following. Examples of the substituent on the fused ring include hydrocarbon groups such as alkyl groups and alkenyl groups, and halogens. R 1 and R 2 and J 1 and J. 2 Examples of the cyclic structure formed by the above include the following structures a to n.

[0052] [ka]

[0053] Among the compounds represented by the above formula (1), compounds represented by any one of the following formulas (1-1) to (1-5) are preferred. Formulas (1-1) to (1-5) are those in which, in formula (1), R 1 and R 2 bond to close the ring, and R 1 and R 2 and J 1 and J. 2 It is a compound that forms a six-membered ring structure containing

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [In the formula, M 1 , L 1 , L 2 , X 1 , X 2 , J 1 , J 2 , A 1 and A 2 is the same as the above formula (1). R 4 represents a substituent present on the 6-membered ring, which may or may not be present, and when present, each independently represents a halogen atom, a hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 9 carbon atoms, a hydrocarbon group having 3 to 9 carbon atoms containing an oxygen atom, a sulfur atom, or a nitrogen atom, a hydrocarbon-substituted silyl group having 1 to 9 carbon atoms, or an amino group optionally substituted with a hydrocarbon group having 1 to 9 carbon atoms. 4 is the R 4 A bridge structure may be formed within the six-membered ring in which R 4 When there are two or more R 4 may form a fused ring sharing some of the constituent atoms of the six-membered ring in which the group is present, or the fused ring may have a substituent. n is R present on the six-membered ring 4 Indicates the number of digits, ranging from 0 to 4.

[0060] Specific examples of halogen atoms include the above L 1 and L 2 Specific examples of halogen atoms described for the substituents of R 4 The following can also be mentioned. Specific examples of the hydrocarbon group having 1 to 9 carbon atoms include the above L 1 and L 2 Among the specific examples of hydrocarbon groups having 1 to 20 carbon atoms explained for the substituents of the formula (1), examples having 1 to 9 carbon atoms are shown as R4 R 4 Specific examples of when is a hydrocarbon group having 1 to 9 carbon atoms include alkyl groups 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, and alkenyl groups having 1 to 4 carbon atoms such as a vinyl group, a propenyl group, and a butenyl group. Specific examples of the alkoxy group having 1 to 9 carbon atoms include the above L 1 and L 2 Among the specific examples of the alkoxy group having 1 to 20 carbon atoms explained for the substituent of the formula (1), examples having 1 to 9 carbon atoms are shown as R 4 R 4 When is an alkoxy group having 1 to 9 carbon atoms, specific examples thereof include alkoxy groups having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group.

[0061] Specific examples of the halogen-substituted hydrocarbon group having 1 to 9 carbon atoms include the above-mentioned L 1 and L 2 Among the specific examples of the halogen-substituted hydrocarbon group having 1 to 20 carbon atoms explained for the substituent of the formula (1), the examples having 1 to 9 carbon atoms are shown as R 4 R 4 When is a halogen-substituted hydrocarbon group having 1 to 9 carbon atoms, specific examples thereof include a trifluoromethyl group and a 2,2,2-trifluoroethyl group. Specific examples of the hydrocarbon group having 3 to 9 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom include the above-mentioned L 1 and L 2 Among the specific examples of hydrocarbon groups containing oxygen atoms, sulfur atoms, or nitrogen atoms and having 3 to 20 carbon atoms as explained for the substituents of the formula (1), examples of hydrocarbon groups containing 3 to 9 carbon atoms are shown as R 4 R 4 When R contains an oxygen atom, specific examples include hydrocarbon groups 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. 4When R contains a sulfur atom, specific examples include hydrocarbon groups having 5 to 8 carbon atoms and containing a sulfur atom, such as a methylthiobutyl group, an ethylthiobutyl group, a methylthiohexyl group, and an ethylthiohexyl group. 4 When the group contains a nitrogen atom, specific examples thereof include hydrocarbon groups having 6 to 8 carbon atoms and containing a nitrogen atom, such as a dimethylaminobutyl group and a dimethylaminohexyl group.

[0062] Specific examples of the hydrocarbon-substituted silyl group having 1 to 9 carbon atoms include the above L 1 and L 2 Among the specific examples of the hydrocarbon-substituted silyl group having 1 to 20 carbon atoms explained for the substituent of the formula (1), the examples having 1 to 9 carbon atoms are shown as R 4 R 4 When is a hydrocarbon-substituted silyl group having 1 to 9 carbon atoms, specific examples thereof include hydrocarbon-substituted silyl groups having 1 to 2 carbon atoms, such as trimethylsilyl and triethylsilyl. Specific examples of the amino group which may be substituted with a hydrocarbon group having 1 to 9 carbon atoms include tertiary amino groups substituted with an alkyl group having 1 to 4 carbon atoms, such as a dimethylamino group, a diethylamino group, and a dibutylamino group.

[0063] In equation (1), M 1 is a zirconium atom, and X 1 and X 2 Specific examples of transition metal compounds in which is a chlorine atom include the following:

[0064] [Table 1-1]

[0065] [Table 1-2]

[0066] M 1Although titanium atoms and hafnium atoms can be used in addition to zirconium atoms, zirconium atoms are preferred. Among the above compounds, J 1 , J 2 , R 1 and R 2 The cyclic structure formed by the above formula is preferably a benzene-1,2-diyl group, i.e., a benzene ring, and the compound numbers 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 19, 20, and 21 in the above table are more preferred, and the compound numbers 5, 6, 7, 10, 11, 14, and 15 are particularly preferred.

[0067] The transition metal compound represented by formula (1) can be produced by utilizing a general method for synthesizing metallocene compounds. A typical procedure involves synthesizing an indenyl lithium salt from indene and butyllithium, then reacting two equivalents of the lithium salt with α,α'-dibromo-orthoxylene to synthesize the metallocene ligand α,α'-bis(1-indenyl)-orthoxylene, which is then further synthesized with butyllithium to form the lithium salt of the ligand, which is then reacted with zirconium tetrachloride to obtain the metallocene. By using various compounds with cyclopentadienyl structures instead of the above indene, L 1 and L 2 It is possible to obtain metallocene compounds with different In addition, when synthesizing the transition metal compound represented by formula (1), Example 1 of JP-A-9-286812 and the synthesis example of compound 1a described in Journal of Organometallic Chemistry 535 (1997) 29-32 can be used as reference. In formula (1), R 1 and R 2 and J 1 and J. 2 When synthesizing a compound in which R 1 and R 2 together form a cyclic structure or the cyclic structure further forms a polycyclic structure, as explained above, 1 and R 2 and J 1 and J.2 A starting compound in which the moiety corresponding to R already forms a monocyclic or polycyclic ring structure may be used, or a compound in which R 1 and R 2 may be reacted to close the ring to form a cyclic structure.

[0068] 2. Component (II) The component (II) used in the present invention is a transition metal compound selected from the group of compounds 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 component (II). Formula (2): A 3 q L 3 L 3’ M 3 X 3 X 3’

[0069] [In the formula, M 3 indicates a transition metal in Group 4 of the periodic table. L 3 and L 3’ each independently represents a ligand containing a cyclopentadienyl structure, M 3 The ligand containing a cyclopentadienyl structure may be substituted with 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 and containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms. 3 or L 3’ When adjacent substituents are present on the aryl group, they may be bonded to form a ring structure. X 3 and X 3’ are each independently, M 3and represents 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, which is bonded to the A 3 L 3 and L 3’ represents a bridging group that bridges L 3 and L 3’ There is a bridge structure between them. q is 0 or 1, and A 3 Indicates the number of

[0070] M 3 is a transition metal in group 4 of the periodic table, and M 3 Examples of the atom include titanium (Ti), zirconium (Zr) and hafnium (Hf), with zirconium being preferred from the viewpoint of high catalyst activity.

[0071] L 3 and L 3’ contains a cyclopentadienyl structure, and M 3 Examples of the ligand containing a cyclopentadienyl structure include a ligand having a cyclopentadinyl skeleton, a ligand having an indenyl skeleton, and a ligand having a fluorenyl skeleton. Ligand L 3 and L 3’ can be the following combinations: ligands each having a substituted or unsubstituted cyclopentadinyl skeleton; ligands each having a substituted or unsubstituted indenyl skeleton; ligands each having a substituted or unsubstituted fluorenyl skeleton; L 3 is a ligand having a substituted or unsubstituted cyclopentadienyl skeleton, and L 3’ L is a ligand having a substituted or unsubstituted indenyl skeleton; 3 is a ligand having a substituted or unsubstituted cyclopentadienyl skeleton, and L 3’ L is a ligand having a substituted or unsubstituted fluorenyl skeleton; 3 is a ligand having a substituted or unsubstituted indenyl skeleton, and L3’ A ligand having a substituted or unsubstituted fluorenyl skeleton. Among these combinations, L 3 , L 3’ and L are both ligands having a substituted or unsubstituted indenyl skeleton; 3 is a ligand having a substituted or unsubstituted cyclopentadienyl skeleton, and 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 preferred.

[0072] Ligand L 3 and L 3’ may be substituted with 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 and containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms. 3 or L 3’ When adjacent substituents are present on the aryl group, they may be bonded to form a ring structure.

[0073] Specific examples of halogen atoms include the above L 1 and L 2 Specific examples of halogen atoms described for the substituents of L 3 and L 3’ The following can also be mentioned. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include the above L 1 and L 2 Specific examples of the hydrocarbon group having 1 to 20 carbon atoms described for the substituent of L 3 and L 3’ The following can also be mentioned. Specific examples of the alkoxy group having 1 to 20 carbon atoms include the above L 1 and L 2 Specific examples of the alkoxy group having 1 to 20 carbon atoms described for the substituent of 3 and L 3’The following can also be mentioned. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms and containing 1 to 6 silicon atoms include the above-mentioned L 1 and L 2 Specific examples of the hydrocarbon group having 1 to 20 carbon atoms and containing 1 to 6 silicon atoms as described for the substituents of 3 and L 3’ The following can also be mentioned.

[0074] Specific examples of the halogen-substituted hydrocarbon group having 1 to 20 carbon atoms include the above-mentioned L 1 and L 2 Specific examples of the halogen-substituted hydrocarbon group having 1 to 20 carbon atoms described for the substituents of 3 and L 3’ The following can also be mentioned. Specific examples of the hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom include the above-mentioned L 1 and L 2 Specific examples of the hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom described for the substituent of 3 and L 3’ The following can also be mentioned. Specific examples of the hydrocarbon-substituted silyl group having 1 to 20 carbon atoms include the above-mentioned L 1 and L 2 Specific examples of the hydrocarbon-substituted silyl group having 1 to 20 carbon atoms described above for the substituents are shown below as L 3 and L 3’ The following can also be mentioned.

[0075] L 3 , L 3’ are both substituted indenyl groups, it is preferred that at least one, and preferably both, of the indenyl groups has an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an optionally substituted furyl group, or an optionally substituted thienyl group at the 2-position. Also preferably used are those in which at least one, preferably both, of the indenyl groups has an aryl group which may have a substituent at the 4-position.

[0076] X 3 and X 3’ are each independently, M 3 is 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, which is bonded to X 3 and X 3’ Specific examples of X in the formula (1) include 1 and X 2 A specific example explaining this is X 3 and X 3’ The following can also be mentioned.

[0077] A 3 L 3 and L 3’ When q in formula (2) is 0 (zero), A 3 does not exist, and L 3 and L 3’ There is no bridge structure between them. The compound of formula (2) may be either an unbridged or bridged metallocene, but is preferably a bridged metallocene.

[0078] Bridging group A 3 is preferably any one of 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 germylene group which may have a substituent. 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, a hydrocarbon group having 1 to 20 carbon atoms and containing 1 to 6 silicon atoms, a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms, and a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom. A 3 When there are multiple substituents on the same, they may be bonded to each other to form a ring structure.

[0079] A 3Specific examples of the alkylene group include alkylene groups such as methylene, methylmethylene, dimethylmethylene, and 1,2-ethylene; aryl alkylene groups such as diphenylmethylene; silylene groups; alkyl silylene groups such as methylsilylene, dimethylsilylene, diethylsilylene, di(n-propyl)silylene, di(i-propyl)silylene, and di(cyclohexyl)silylene; (alkyl)(aryl)silylene groups such as methyl(phenyl)silylene; aryl silylene groups such as diphenylsilylene; alkyl oligosilylene groups such as tetramethyldisilylene; germylene groups; alkylgermylene groups in which the silicon of the above alkylsilylene groups is substituted with germanium; (alkyl)(aryl)germylene groups; and arylgermylene groups. In addition, when a ring structure is formed, examples of the ring structure include divalent groups having a 4- to 7-membered ring structure such as silacyclobutane, silacyclopentane, 2,5-dimethylsilacyclopentane, silacyclohexane, and silafluorene. Among these, a silylene group having a hydrocarbon group with 1 to 20 carbon atoms or a germylene group having a hydrocarbon group with 1 to 20 carbon atoms is preferred, with an alkylsilylene group and an alkylgermylene group being particularly preferred.

[0080] Among the transition metal compounds represented by formula (2), the transition metal compound represented by the following formula (2-1) is preferred.

[0081] [ka]

[0082] [In the formula, M 3 represents a titanium atom (Ti), a zirconium atom (Zr), or a hafnium atom (Hf). X 3 and X 3’ are the X in the formula (2), respectively. 3 and X 3’ is the same as Y represents a carbon atom, a silicon atom, or a germanium atom. R 11 and R21 R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an optionally substituted furyl group, or an optionally substituted thienyl group. 11 and R 21 At least one of the groups is either an optionally substituted furyl group or an optionally substituted thienyl group. 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 R each independently represents 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, an alkyl group having 1 to 6 carbon atoms and having a trialkylsilyl 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 heterocyclic group forming a 5- or 6-membered ring which may have a substituent. 12 ~R 19 and R 22 ~R 29 Adjacent groups among these may be bonded to each other to form a 6- or 7-membered ring, and the 6- or 7-membered ring may contain an unsaturated bond. R 31 and R 32 R each independently represents 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, an alkyl group having 1 to 6 carbon atoms and having a trialkylsilyl 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 heterocyclic group forming a 5- or 6-membered ring which may have a substituent. 31 and R 32may form a 4- to 7-membered ring together with Y, and R 31 and R 32 When at least one of R 31 and R 32 and Y are 4 to 7 membered rings, 31 and R 32 may form a fused ring sharing some of the constituent atoms of the cyclic structure of

[0083] Among the transition metal compounds represented by formula (2), the following are preferred. (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-phenanthryl)indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-methyl-4-(4-chloro-2-naphthyl)indenyl}]zirconium dichloride,

[0084] [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'-dimethylgermylenebis{2-methyl-4-(2-fluoro-4-biphenyl)indenyl}]zirconium dichloride, [1,1'-dimethylgermylenebis{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,

[0085] Furthermore, as a compound in which the 2-position of the indenyl group is a furyl 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'-diphenylsilylenebis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]zirconium dichloride, [1,1'-dimethylgermylenebis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]zirconium dichloride, [1,1'-dimethylgermylenebis{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,

[0086] [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,

[0087] [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-phenanthryl)-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(9-phenanthryl)-indenyl}]zirconium dichloride,

[0088] [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-phenanthryl)-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-furyl)-4-(2-phenanthryl)-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(9-phenanthryl)-indenyl}]zirconium dichloride, and the like.

[0089] (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, isopropylidene(1-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, isopropylidene(1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconium dichloride, Examples include diphenylsilanediyl(1-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, dimethylsilanediyl(1-cyclopentadienyl)(9-fluorenyl)zirconium dichloride, and the like.

[0090] (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-difluorenyl)ethane zirconium dichloride, (1,3-difluorenylpropane)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.

[0091] To prepare the transition metal compound represented by formula (2), a compound with a cyclopentadiene structure, which is the base of the ligand structure, is synthesized, and the lithium salt of the ligand is prepared using butyllithium or similar. Two equivalents of the lithium salt are reacted with dimethyldichlorosilane to synthesize a bridged ligand. This bridged ligand is then reacted with two equivalents of butyllithium to form a dilithium salt, which is then reacted with zirconium tetrachloride to obtain a bridged metallocene compound. Various metallocene compounds can be obtained by using cyclopentadiene, indene, or fluorene, each of which has a substituent attached to the initial cyclopentadiene structure. Alternatively, a ligand with a different structure bridged to it can be obtained by reacting the lithium salt of the ligand with one equivalent of dimethyldichlorosilane and then reacting it with the lithium salt of another ligand.

[0092] [Compound of formula (3)] In the present invention, a transition metal compound represented by the following formula (3) can be used as component (II). Formula (3): A 4 L 4 M 4 X 4 X 4’

[0093] [In the formula, M 4 indicates a transition metal in Group 4 of the periodic table. L 4 indicates a ligand containing a cyclopentadienyl structure, and M 4 The ligand containing a cyclopentadienyl structure may be substituted with 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 and containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom, or a silyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms. X 4 and X 4’ are each independently a metal M 4and represents 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, which is bonded to the A 4 L 4 represents an organic group having a heteroatom bonded to M via the heteroatom 4 is bonded to.]

[0094] M 4 is a transition element in group 4 of the periodic table. 4 Examples of the atoms that can be used include titanium atoms (Ti), zirconium atoms (Zr) and hafnium atoms (Hf), with titanium atoms being preferred. L 4 contains a cyclopentadienyl structure, and M 4 Examples of the ligand containing a cyclopentadienyl structure include a ligand having a cyclopentadinyl skeleton, a ligand having an indenyl skeleton, and a ligand having a fluorenyl skeleton. Ligand L 4 may be substituted with 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 and containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms. Ligand L 4 Specific examples of the substituents include the ligand L of the transition metal compound represented by the formula (2). 3 A specific example explaining 4 The following can also be mentioned.

[0095] X 4 and X 4’ are each independently, M 4is 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, which is bonded to X 4 and X 4’ Specific examples of X in the formula (1) include 1 and X 2 A specific example explaining this is X 4 and X 4’ The following can also be mentioned.

[0096] A 4 L 4 is an organic group having a heteroatom bonded to M through the heteroatom 4 In this case, A 4 L 4 and the heteroatom-containing moiety Z, which can be written as QZ. Examples of Q in the QZ structure include 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, and a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. Specific examples include a dimethylsilylene group, a diethylsilylene group, a di-i-propylsilylene group, a diphenylsilylene group, a methylphenylsilylene group, a methyl-i-propylsilylene group, a dimethylgermylene group, a diethylgermylene group, a di-i-propylgermylene group, a diphenylgermylene group, a methylphenylgermylene group, a methyl-i-propylgermylene group, a dimethylmethylene group, an ethylene group, a 1,2-dimethylethylene group, a 1-phenylethylene group, a 1,2-diphenylethylene group, a silacyclobutane group, a silacyclopentane group, a 2,5-dimethylsilacyclopentane group, a silacyclohexane group, a silafluorene group, and a phenylene group. Among these, dimethylsilylene group, di-i-propylsilylene group, diphenylsilylene group, silacyclobutane group, silacyclopentane group, silacyclohexane group, and phenylene group are preferred, and dimethylsilylene group, diphenylsilylene group, and silacyclohexane group are particularly preferred. Z in the QZ structure may be 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, or an oxygen atom, and most preferably an amide group.

[0097] To produce the transition metal compound represented by formula (3), a metal salt of a compound with a cyclopentadiene structure is prepared, and then reacted with dichlorodialkylsilane to produce a compound in which a dialkylchlorosilane is bonded to the compound with a cyclopentadiene structure. Next, by reacting with amines, this is converted into an amino(dialkyl)silane group, which is then converted into a lithium salt by the action of butyllithium, and then reacted with titanium tetrachloride to produce a complex in which the Cp compound -SiR2-(NR) is coordinated. In this case, by changing the types of the cyclopentadiene compound and amine compound used as raw materials, various transition metal compounds of formula (3) can be produced.

[0098] [Compound of formula (4)] In the present invention, a transition metal compound represented by the following formula (4) can be used as component (II). Formula (4): L 5 m M 5 X 5 p

[0099] [In the formula, M 5 indicates a transition metal in groups 3 to 11 of the periodic table. m L's 5 each independently represents a hydrocarbon group substituted with a substituent having two or more atoms selected from oxygen, nitrogen, phosphorus, and sulfur atoms, and at least two of the atoms selected from oxygen, nitrogen, phosphorus, and sulfur atoms are M 5 is bonded to. p pieces of X 5 are each independently, M 5represents 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 containing an oxygen atom or a nitrogen atom, or a neutral Lewis base, which is bonded to m is L 5 indicates the number of p represents the number of X, and is a number selected so that the transition metal compound of formula (4) is electrically neutral.

[0100] M 5 is a transition element in groups 3 to 11 of the periodic table. 5 Examples of the metal atom 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, a yttrium atom, a chromium atom, a molybdenum atom, a tungsten atom, a manganese atom, a rhenium atom, an iron atom, a ruthenium atom, an osnium atom, and an iridium atom. Preferred are a scandium atom, a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a niobium atom, a tantalum atom, a cobalt atom, and a rhodium atom. More preferred are a titanium atom, a zirconium atom, a hafnium atom, a cobalt atom, a rhodium atom, a vanadium atom, a niobium atom, and a tantalum atom. Particularly preferred are a titanium atom, a zirconium atom, and a hafnium atom.

[0101] L 5 Specific examples of the transition metal compound represented by formula (4) include the groups represented by formula (L5-1), formula (L5-2), formula (L5-3), formula (L5-4), and formula (L5-5) described below. These will be described later as specific examples of the transition metal compound represented by formula (4). X 5 Specific examples of X in the formula (1) include 1 and X 2 A specific example explaining this is X 5 The following can also be mentioned.

[0102] Specific examples of the transition metal compound represented by formula (4) include groups represented by the following formulae (4-1), (4-2), (4-3), (4-4) and (4-5). Among these, the compounds of formula (4-2) and formula (4-4) are preferred because they have an appropriate difference in molecular weight when combined with component (I).

[0103] [Transition metal compound represented by formula (4-1)] The transition metal compound represented by formula (4-1) is represented by L 5 has a substituent represented by formula (L5-1).

[0104] [ka]

[0105] [ka]

[0106] [In formula (4-1) and formula (L5-1), M 5 represents a transition metal atom of Groups 3 to 6 of the periodic table. X 5 are each independently 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 and containing an oxygen atom or a nitrogen atom. p is M 5 The valence is -2. R 51 and R 52 each independently represents a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an organic silyl group, or a substituent having at least one element selected from a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, and a silicon atom. m is an integer of 0 to 2, and n is an integer of 1 to 5. A represents an atom of groups 13 to 16 of the periodic table. When n is 2 or more, the multiple As may be the same or different. E represents a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron, and silicon atoms. When m is 2 or more, the multiple E's may be the same or different, and two or more groups represented by E's may be linked to each other to form a ring.

[0107] R 51 and R 52 is a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an organic silyl group, or a substituent having at least one element selected from a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, and a silicon atom. Examples of hydrocarbon groups include linear or branched alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, and t-butyl; aryl groups having 6 to 20 carbon atoms, such as phenyl and naphthyl; substituted aryl groups in which these aryl groups are substituted with 1 to 5 substituents, such as the above-mentioned alkyl groups having 1 to 20 carbon atoms; cycloalkyl groups such as cyclopentyl and norbornyl; alkenyl groups such as vinyl, propenyl, and cyclohexenyl; and arylalkyl groups such as benzyl, phenylethyl, and phenylpropyl. Examples of halogenated hydrocarbon groups include groups in which the above hydrocarbon groups are substituted with halogen. Examples of the organic silyl group include a methylsilyl group, a trimethylsilyl group, an ethylsilyl group, and a triphenylsilyl group. Examples of hydrocarbon groups 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 groups in which the above hydrocarbon groups are substituted with -COOCH3, -N(CH3)C(O)CH3, -OC(O)CH3, -CN, -N(C2H5)2, -N(CH3)S(O2)CH3, -P(C6H5)2, etc.

[0108] A is an atom of Groups 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 carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron, and silicon atoms. Examples of the linking group linking two nitrogen atoms represented by -((E m)A)n- include the following groups: -CH2-, -C(Me)2-, -C(Ph)2-, -Si(Me)2-, -Si(Ph)2-, -Si(Me)(Ph)-, -CH2CH2CH2-, -CH2C(nPr)2CH2-, and -CH2C(cHex)2CH2-.

[0109] The transition metal compound represented by the above formula (4-1) is similar to compound (I-1) in JP-A-10-330412, and this publication can be used as a reference.

[0110] [Transition metal compound represented by formula (4-2)] The transition metal compound represented by formula (4-2) is L 5 has a substituent represented by formula (L5-2).

[0111] [ka]

[0112] [ka]

[0113] [In formula (4-2) and formula (L5-2), M 5 represents a transition metal atom of Groups 3 to 11 of the periodic table. m represents an integer of 1 or 2. R 53 ~R 58each independently represents 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, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring. n is M 5 indicates the number that satisfies the valence of X 5 each independently represents 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 and containing an oxygen atom or a nitrogen atom.]

[0114] R 53 ~R 58 is 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, a germanium-containing group, or a tin-containing group.

[0115] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of hydrocarbon groups include linear or branched alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, and t-butyl; linear or branched alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, and isopropenyl; linear or branched alkynyl groups having 2 to 30 carbon atoms, such as propargyl; saturated cyclic hydrocarbon groups having 3 to 30 carbon atoms, such as cyclohexyl and adamantyl; unsaturated cyclic hydrocarbon groups having 5 to 30 carbon atoms, such as cyclopentadienyl, indenyl, and fluorenyl; aromatic groups having 6 to 30 carbon atoms, such as phenyl, benzyl, naphthyl, and biphenyl; and alkyl-substituted aromatic groups, such as tolyl, t-butylphenyl, and di-t-butylphenyl. The hydrocarbon group may be substituted with a halogen atom such as a fluorine atom; another hydrocarbon group; a heterocyclic compound residue described below, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. Examples of heterocyclic compound residues include residues of nitrogen-containing compounds such as pyrrole groups and pyridine groups, oxygen-containing compounds such as furan groups and pyran groups, and sulfur-containing compounds such as thiophene groups, as well as groups in which these heterocyclic compound residues are further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30 carbon atoms.

[0116] Examples of oxygen-containing groups include alkoxy groups, aryloxy groups, ester groups, ether groups, and acyl groups. Examples of the nitrogen-containing group include an amino group, an imino group, an amido group, a hydrazino group, a nitro group, and a cyano group. Examples of the boron-containing group include a boranediyl group, a boranetriyl group, and a diboranyl group. Examples of sulfur-containing groups include a mercapto group, a thioester group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, a sulfo group, and a sulfonyl group. Examples of phosphorus-containing groups include phosphido groups, phosphoryl groups, thiophosphoryl groups, and phosphato groups. Examples of silicon-containing groups include silyl groups; siloxy groups; hydrocarbon-substituted silyl groups such as methylsilyl groups, trimethylsilyl groups, triethylsilyl groups, triphenylsilyl groups, and dimethylphenylsilyl groups; and hydrocarbon-substituted siloxy groups such as trimethylsiloxy groups. Examples of the germanium-containing group and the tin-containing group include the above silicon-containing groups in which silicon is substituted with germanium and tin.

[0117] The transition metal compound represented by the above formula (4-2) is similar to the transition metal compound (B) represented by general formula (I) in JP-A No. 2000-63415, and this publication can be used as a reference.

[0118] [Transition metal compound represented by formula (4-3)] The transition metal compound represented by formula (4-3) is represented by L 5 has a substituent represented by formula (L5-3).

[0119] [ka]

[0120] [ka]

[0121] [In formula (4-3) and formula (L5-3), M 5 indicates a transition metal atom of Groups 8 to 11 of the periodic table. R 61 ~R 64 each independently represents a hydrogen atom, 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, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, a tin-containing group, or the like. R 65 and R 66 are each independently 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, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, a tin-containing group, or the like. 61 and R 65 may be linked to each other to form a ring, R 62 and R 66 may be linked to each other to form a ring, R 61 and R 63 may be linked to each other to form a ring, and R 62 and R 64 may be linked to each other to form a ring, R 63 and R 64 may be linked to each other to form a ring. n is M 5 indicates the valence of. X 5 represents 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 and containing an oxygen atom or a nitrogen atom. If n is 2 or more, X 5 The groups represented by may be the same or different. Y represents an atom in group 15 or 16 of the periodic table.

[0122] R 61 ~R 64 , R 65 and R 66 Specific examples of the 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 or tin-containing group include R 53 ~R 58 A specific example of the explanation is given in R of formula (4-3). 61 ~R 64 , R 65 and R 66 The following can also be mentioned.

[0123] The transition metal compound represented by the above formula (4-3) is similar to the transition metal imine compound represented by general formula (I) in JP-A No. 2000-191719, and this publication can be used as a reference.

[0124] [Transition metal compound represented by formula (4-4)] The transition metal compound represented by formula (4-4) is represented by L 5 has a substituent represented by formula (L5-4).

[0125] [ka]

[0126] [ka]

[0127] [In formula (4-4) and formula (L5-4), R 67 and R 68are each independently an alkyl group, an aryl group, a heterocyclic group, or a hydrogen atom. R 69 and R 70 are each independently a halogen atom, a hydrogen atom, an alkyl having 1 to 20 carbon atoms, an aryl, an alkenyl, an alkylaryl, an arylalkyl, a hydrocarboxy group, an amide, a phosphide, a sulfide, a silylalkyl, a diketonate, or a carboxylate. each X 5 each independently represents 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 and containing an oxygen atom or a nitrogen atom.]

[0128] 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 JP-A-2003-515628, and this publication can be used as a reference. In addition, compound 1 described in paragraph 0030 and compound 2 described in paragraph 0031 of this publication can be used as the transition metal compound of formula (4-4) in the present invention.

[0129] [Transition metal compound represented by formula (4-5)] The transition metal compound represented by formula (4-5) is represented by L 5 has a substituent represented by formula (L5-5).

[0130] [ka]

[0131] [ka]

[0132] [In formula (4-5) and formula (L5-5), n is 1, 2, or 3. M 5 indicates a zirconium atom or a hafnium atom. R71 ~R 78 are each independently 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom. X 5 each independently represents 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 and containing an oxygen atom or a nitrogen atom; X 5L denotes a neutral Lewis base. X 5L If there are multiple X 5L may be the same or different. l is 0, 1, or 2.]

[0133] R 71 ~R 78 is 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms. Examples of hydrocarbon groups having 1 to 20 carbon atoms include linear or branched alkyl groups such as methyl, ethyl, and t-butyl groups; linear or branched alkenyl groups such as vinyl, allyl, and isopropenyl groups; linear or branched alkynyl groups such as propargyl groups; cyclic saturated hydrocarbon groups such as cyclohexyl and adamantyl groups; cyclic unsaturated hydrocarbon groups such as cyclopentadienyl, indenyl, and fluorenyl groups; aromatic groups such as phenyl, benzyl, naphthyl, and biphenyl groups; and alkyl-substituted aromatic groups such as tolyl, t-butylphenyl, and di-t-butylphenyl groups.

[0134] Examples of the hydrocarbon group having 1 to 20 carbon atoms and containing an oxygen atom include hydrocarbon groups having an oxygen-containing group such as an alkoxy 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 and containing a nitrogen atom include hydrocarbon groups having a nitrogen-containing group such as an amino group, an imino group, an amido group, a hydrazino group, a nitro group, and a cyano group. Examples of the hydrocarbon group having 1 to 20 carbon atoms and substituted with a halogen include a trifluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, and a pentafluorophenyl group.

[0135] 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 JP-A-2013-53308, and this publication can be used as a reference.

[0136] II. Olefin polymerization catalysts The above-mentioned component (I) and the above-mentioned component (II) are each catalytically active components for olefin polymerization, and a combination of these components acts as a catalytically active component for an olefin polymerization catalyst capable of producing an olefin polymer having a sufficiently broad 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. The above component (I) and the above component (II) can be combined with a cocatalyst and a carrier to form an olefin polymerization catalyst. In the present invention, for example, an olefin polymerization catalyst containing the following components (I), (II), (III), and (IV) as essential components can be used. Two or more of each component may be used. Component (I): A transition metal compound represented by the above formula (1) Component (II): A transition metal compound selected from the group of compounds represented by the above formula (2), (3) or (4). Component (III): A compound that reacts with the transition metal compounds of components (I) and (II) to generate a cationic compound. Component (IV): Microparticle carrier

[0137] Components (I) and (II) are as described above. Components (III) and (IV) will be described below. 1.Component (III) Component (III), i.e., a compound that reacts with the transition metal compounds of components (I) and (II) to produce a cationic compound, is a co-catalyst. Examples of component (III) that can be used include organoaluminum oxy compounds, borane compounds, borate compounds, and layered silicates (described below). Of these, borane and borate compounds are difficult to immobilize on a fine particle support, and therefore organoaluminum oxy compounds are preferably used.

[0138] (1) Organoaluminum oxy compounds The organoaluminum oxy compound is a compound having Al-O-Al bonds in the molecule, and the number of Al-O-Al bonds is usually in the range of 1 to 100, preferably 1 to 50. Typically, an organoaluminum oxy compound containing a chain structure of -(O-Al)- units, such as that represented by the following formula (5-1) or formula (5-2), is used.

[0139] [ka]

[0140] [ka]

[0141] [In each of the above formulas, R 41 are each independently a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 18 carbon atoms, more preferably a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, an alkenyl group, an aryl group, or an aralkyl group; R 41 At least a part of the groups is a hydrocarbon group. p represents an integer of 0 to 40, preferably 2 to 30.]

[0142] Such organoaluminum oxy-compounds are usually obtained by reacting an organoaluminum compound with water. The reaction of organoaluminum with water is usually carried out in an inert hydrocarbon (solvent), which may be an aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, or xylene, but is preferably an aliphatic hydrocarbon or aromatic hydrocarbon.

[0143] As the organoaluminum compound used as the 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 formula (6), R 41 is the same as the above formulas (5-1) and (5-2), and X 6 represents a hydrogen atom or a halogen atom, and t represents an integer of 1≦t≦3.

[0144] The alkyl group of the trialkylaluminum may be any of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, octyl, decyl, and dodecyl groups, with methyl being particularly preferred. Two or more of the above organoaluminum compounds can also be used in combination.

[0145] The reaction ratio of water to organoaluminum compound (water / Al molar ratio) is 0.25 / 1 to 1.2 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. The water required for the reaction may be not only water but also water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate, etc., or a component that can generate water in the reaction system.

[0146] Organoaluminum oxy compounds using trimethylaluminum as the starting organoaluminum compound are called methylaluminoxane (MAO) and are particularly preferred. MAO can also be used as component (III) in a form containing unreacted trimethylaluminum. This unreacted trimethylaluminum is present in an amount of 1 to 30 mol% relative to the total aluminum atoms of trimethylaluminum and methylaluminoxane. If the amount is too low, MAO precipitates in the solution, making it difficult to use, while if the amount of trimethylaluminum is too high, it becomes difficult to handle. A MAO solution containing 10 to 15 mol% trimethylaluminum is preferred. Furthermore, if the MAO concentration is too high, it becomes dangerous to handle and precipitates during storage, making it difficult to use. Diluting the MAO concentration increases safety and reduces the risk of precipitation, but requires larger containers and equipment, which is economically disadvantageous. The MAO concentration is preferably 10 to 20% by mass. Furthermore, because MAO solutions are prone to precipitation at ambient temperatures, low-temperature storage below -10°C is recommended. Of course, two or more of the above-mentioned organoaluminum oxy compounds may be used in combination as the organoaluminum oxy compound, or the organoaluminum oxy compound may be used in the form of a solution or dispersion in the above-mentioned inert hydrocarbon solvent.

[0147] (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(perfluoroanthryl)borane, and tris(perfluorobinaphthyl)borane.

[0148] 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, and tris(perfluorobinaphthyl)borane are more preferred. Among these, the following compounds are more preferred: tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, and tris(perfluorobiphenyl)borane.

[0149] (3) Borate compounds A first example of the borate compound is a compound represented by the following formula (7). [L 6 -H] + [BR 42 R 43 X 7 X 7’ ] - Formula (7)

[0150] In formula (7), L 6is a neutral Lewis base, H is a hydrogen atom, and [L 6 -H ] is a Bronsted acid such as ammonium, anilinium, or phosphonium. Examples of 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 anilinium include N,N-dialkylanilinium such as N,N-dimethylanilinium, N,N-diethylanilinium, and N,N-2,4,6-pentamethylanilinium. Further, examples of the phosphonium include triarylphosphoniums and trialkylphosphoniums such as triphenylphosphonium, tributylphosphonium, tri(methylphenyl)phosphonium, and tri(dimethylphenyl)phosphonium.

[0151] In addition, in 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, which may be linked to each other via a crosslinking group, and the substituent of the substituted aromatic hydrocarbon group is preferably an alkyl group typified by a methyl group, an ethyl group, a propyl group, an isopropyl group, etc., or a halogen atom such as fluorine, chlorine, bromine, or iodine. Additionally, X 7 and X 7’ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substituted hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with a halogen atom.

[0152] Specific examples of the compound represented by the general formula (7) include the following compounds: tributylammonium tetra(pentafluorophenyl)borate, tributylammonium tetra(2,6-ditrifluoromethylphenyl)borate, tributylammonium tetra(3,5-ditrifluoromethylphenyl)borate, tributylammonium tetra(2,6-difluorophenyl)borate, tributylammonium tetra(perfluoronaphthyl)borate, dimethylanilinium tetra(pentafluorophenyl)borate, dimethylanilinium tetra(2,6-ditrifluoromethylphenyl)borate, dimethylanilinium tetra(3 ,5-ditrifluoromethylphenyl)borate, dimethylanilinium tetra(2,6-difluorophenyl)borate, dimethylanilinium tetra(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, tripropylammonium tetra(perfluoronaphthyl)borate, di(1-propyl)ammonium tetra(pentafluorophenyl)borate, dicyclohexylammonium tetraphenylborate.

[0153] 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)borate, and dimethylanilinium tetra(perfluoronaphthyl)borate.

[0154] A second example of the borate compound is a compound represented by the following formula (8). Formula (8): [L 7 ] + [BR 42 R 43 X 7’ X 7’ ] -

[0155] In formula (8), L 7 Examples of R include 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 cation, and proton. 42 , R 43 , X 7 and X 7’ is the same as defined in the above formula (7).

[0156] Specific examples of the compound represented by the above formula (8) include the following compounds: trityl tetraphenylborate, trityl tetra(o-tolyl)borate, trityl tetra(p-tolyl)borate, trityl tetra(m-tolyl)borate, trityl tetra(o-fluorophenyl)borate, trityl tetra(p-fluorophenyl)borate, trityl tetra(m-fluorophenyl)borate, trityl tetra(3,5-difluorophenyl)borate, trityl tetra(pentafluorophenyl)borate, trityl tetra(2,6-ditrifluoromethylphenyl)borate, trityl tetra(3,5-ditrifluoromethylphenyl)borate, trityl tetra(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-ditrifluoro methylphenyl)borate, tropinium tetra(perfluoronaphthyl)borate, NaBPh4, NaB(o-CH3-Ph)4, NaB(p-CH3-Ph)4, NaB(m-CH3-Ph)4, NaB(oF-Ph)4, NaB(pF-Ph)4, NaB(mF-Ph)4, NaB(3,5-F2-Ph)4, NaB(C6F5)4, NaB(2,6-(CF3)2-Ph)4, NaB(3,5-(CF3)2-Ph)4, NaB(C 10 F7)4, HBPh4·(Et2O)2, HB(3,5-F2-Ph)4·(Et2O)2, HB(C6F5)4·(Et2O)2, HB(2,6-(CF3)2-Ph)4·(Et2O)2, HB(3,5-(CF3)2-Ph)4·(Et2O)2, HB(C 10 H7)4·(Et2O)2.

[0157] Among these, the following compounds are preferred: trityl tetra(pentafluorophenyl)borate, trityl tetra(2,6-ditrifluoromethylphenyl)borate, trityl tetra(3,5-ditrifluoromethylphenyl)borate, trityl tetra(perfluoronaphthyl)borate, tropinium tetra(pentafluorophenyl)borate, tropinium tetra(2,6-ditrifluoromethylphenyl)borate, tropinium tetra(3,5-ditrifluoromethylphenyl)borate, tropinium tetra(perfluoronaphthyl)borate, NaB(CF), NaB(2,6-(CF-Ph), NaB(3,5-(CF-Ph), NaB(CF 10 F7)4, HB(C6F5)4·(Et2O)2, HB(2,6-(CF3)2-Ph)4·(Et2O)2, HB(3,5-(CF3)2-Ph)4·(Et2O)2, HB(C 10 H7)4·(Et2O)2.

[0158] Among these, the following compounds are more preferred: trityl tetra(pentafluorophenyl)borate, trityl tetra(2,6-ditrifluoromethylphenyl)borate, tropinium tetra(pentafluorophenyl)borate, tropinium tetra(2,6-ditrifluoromethylphenyl)borate, NaB(C6F5)4, NaB(2,6-(CF3)2-Ph)4, HB(C6F5)4·(Et2O)2, HB(2,6-(CF3)2-Ph)4·(Et2O)2, HB(3,5-(CF3)2-Ph)4·(Et2O)2, HB(C 10 H7)4·(Et2O)2.

[0159] As component (III), a mixture of the organoaluminum oxy compound and the borane compound or borate compound can be used. Furthermore, two or more of the borane compounds or borate compounds can be mixed and used.

[0160] 2. Component (IV) Component (IV), i.e., the particulate carrier, can be an inorganic carrier, a particulate polymer carrier, or a mixture thereof. The inorganic carrier can be a metal, a metal oxide, a metal chloride, a metal carbonate, a carbonaceous material, or a mixture thereof. Suitable metals that can be used for the inorganic support include, for example, iron, aluminum, nickel, and the like.

[0161] Metal oxides include single oxides or composite oxides of elements from Groups 1 to 14 of the Periodic Table, such as SiO2, Al2O3, MgO, CaO, BO3, TiO2, ZrO2, Fe2O3, Al2O3·MgO, Al2O3·CaO, Al2O3·SiO2, Al2O3·MgO·CaO, Al2O3·MgO·SiO2, Al2O3·CuO, Al2O3·Fe2O3, Al2O3·NiO, and SiO2·MgO. The above formulas are not molecular formulas but represent only the composition, and the structure and component ratios of the composite oxides used in the present invention are not particularly limited. The metal oxides used in the present invention may absorb small amounts of moisture and may contain small amounts of impurities.

[0162] As the metal chloride, for example, chlorides of alkali metals and alkaline earth metals are preferred, and specifically, MgCl, CaCl, etc. are particularly preferred. As the metal carbonate, carbonates of alkali metals and alkaline earth metals are preferred, and specifically, magnesium carbonate, calcium carbonate, barium carbonate, etc. are included. Examples of carbonaceous materials include carbon black and activated carbon. Although any of the above inorganic carriers can be suitably used in the present invention, 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 silica having an average particle size of about 10 μm to 150 μm. Here, the average particle size is a value indicated as a median diameter based on data expressed on a volume basis using a commonly used measurement method using laser diffraction.

[0163] These inorganic supports are preferably used after being calcined in air or in an inert gas such as nitrogen or argon at 200 to 800°C, preferably 400 to 600°C, to adjust the amount of surface hydroxyl groups to 0.8 mmol / g to 1.5 mmol / g. The properties of these inorganic supports are not particularly limited, but the average particle size is usually 5 μm to 200 μm, preferably 10 μm to 150 μm, the average pore size 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 is 0.3 cm 3 / g~2.5cm 3 / g, preferably 0.5 cm 3 / g~2.0cm 3 / g, apparent specific gravity is 0.20g / cm 3 ~0.50g / cm 3 , preferably 0.25 g / cm 3 ~0.45g / cm 3 It is preferable to use an inorganic carrier having the following formula:

[0164] The inorganic supports described above can be used as they are, but they can also be used after being pretreated by contacting them with an organoaluminum compound such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum, or diisobutylaluminum hydride, or an organoaluminum oxy compound containing an Al-O-Al bond.

[0165] III. Preparation of olefin polymerization catalysts An olefin polymerization catalyst containing component (I) and component (II) as catalytically active components can be prepared by mixing component (I) and component (II), and, if necessary, a cocatalyst such as component (III) and component (IV), and a support. When preparing an olefin polymerization catalyst containing component (I) and component (II), the method for contacting component (I) and component (II) with a cocatalyst and a support is not particularly limited. For example, when component (I) and component (II) are contacted with component (III) and component (IV), the following methods can be optionally adopted. Method (1): Components (I) and (II) are first contacted with component (III) and then contacted with component (IV). More specifically, components (I) and (II) are contacted with one component (III), or components (I) and (II) are each contacted with a separate component (III), and the resulting contact-treated product is then contacted with component (IV). When component (I) and component (II) are contacted with one component (III), a mixture of component (I) and component (II) may be contacted with component (III), or component (I) and component (II) may be contacted with component (III) simultaneously or sequentially. When component (I) and component (II) are each contacted with a separate component (III), a contact-treated product of component (I) and a contact-treated product of component (II) may be contacted with a single component (IV), or a contact-treated product of component (I) and a contact-treated product of component (II) may each be contacted with a separate component (III), and then the two resulting contact-treated products may be mixed.

[0166] Method (2): Components (I) and (II) are first contacted with component (IV) and then contacted with component (III). More specifically, components (I) and (II) are contacted with one component (IV), or components (I) and (II) are each contacted with a separate component (IV), and the resulting contact-treated product is then contacted with component (III). When component (I) and component (II) are contacted with one component (IV), a mixture of component (I) and component (II) may be contacted with component (IV), or component (I) and component (II) may be contacted with component (IV) simultaneously or sequentially. When component (I) and component (II) are each contacted with a separate component (IV), a contact-treated product of component (I) and a contact-treated product of component (II) may be contacted with a single component (III), or a contact-treated product of component (I) and a contact-treated product of component (II) may each be contacted with a separate component (III), and then the two resulting contact-treated products may be mixed.

[0167] Method (3): After component (III) and component (IV) are first contacted to obtain a contact-treated product, components (I) and (II) are contacted with the contact-treated product. More specifically, after component (III) and component (IV) are contacted to obtain a contact-treated product, components (I) and (II) are contacted with one contact-treated product, or components (I) and (II) are each contacted with a separate contact-treated product, and the two resulting contact-treated products are mixed. When component (I) and component (II) are contacted with one contact-treated product, a mixture of component (I) and component (II) may be contacted with the contact-treated product, or component (I) and component (II) may be contacted with the contact-treated product simultaneously or sequentially.

[0168] Among these contact methods, method (1) in which component (I) and component (II) are first contacted with component (III), and method (3) in which component (I) and component (II) are contacted with a contact-treated product of component (III) and component (IV) are preferred, with method (1) being the most preferred. Furthermore, it is preferred to contact a mixture of component (I) and component (II) with component (III), component (IV), or a contact-treated product of component (III) and component (IV).

[0169] In any of the contacting methods, the components are usually contacted with each other in an inert atmosphere such as nitrogen or argon, with or without stirring, in the presence of a liquid inert hydrocarbon, such as an aromatic hydrocarbon (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene, or ethylbenzene, or an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as heptane, hexane, decane, dodecane, or cyclohexane. This contact is desirably carried out at a temperature of usually -100°C to 200°C, preferably -50°C to 100°C, and more preferably 0°C to 50°C, for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, and more preferably 30 minutes to 12 hours. A specific example of the contacting method is a method in which a mixture of component (I) and component (II), or a liquid in which component (I) and component (II) are dissolved or dispersed in an inert solvent as described above, is mixed with a liquid in which component (III) is dissolved or dispersed in an inert solvent, and the resulting mixture is mixed with a slurry of component (IV).

[0170] Furthermore, when component (I), component (II), component (III), and component (IV) are brought into contact with each other, it is possible to use either an aromatic hydrocarbon solvent in which some components are soluble or slightly soluble, or an aliphatic or alicyclic hydrocarbon solvent in which some components are insoluble or slightly soluble.

[0171] When the contact reactions of the components are carried out stepwise, the solvent used in the previous step may be used as it is in the subsequent contact reaction without removing it. Alternatively, after the previous contact reaction using a soluble solvent, a liquid inert hydrocarbon in which certain components are insoluble or poorly soluble (e.g., an aliphatic, alicyclic, or aromatic hydrocarbon such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, or xylene) may be added to recover the desired product as a solid. Alternatively, after partially or completely removing the soluble solvent by drying or other means to recover the desired product as a solid, the subsequent contact reaction of this desired product may be carried out using one of the above-mentioned inert hydrocarbon solvents. In the present invention, the contact reactions of the components may be carried out multiple times.

[0172] In the present invention, the proportions of component (I), component (II), component (III) and component (IV) used are not particularly limited, but the following ranges are preferred. The molar ratio of component (I) to component (II) (component (I):component (II)) is adjusted as desired to determine the shape of the molecular weight distribution of the resulting polymer, and is generally in the range of 1:500 to 500:1, preferably 1:100 to 100:1, and more preferably 1:10 to 10:1. When an organoaluminum oxy compound is used as component (III), the molar ratio (Al / M) of aluminum atoms in the organoaluminum oxy compound to the total amount of transition metal (M) contained in components (I) and (II) is generally 1 to 100,000, preferably 5 to 1,000, and more preferably 50 to 200. When a borane compound or a borate compound is used, the molar ratio (B / M) of boron atoms to the total amount of transition metal (M) contained in components (I) and (II) is generally 0.01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10. Furthermore, when a mixture of an organoaluminum oxy-compound, a borane compound, and a borate compound is used as component (III), it is desirable to select the use ratio of each compound in the mixture in the same manner as above relative to the total amount of the transition metal (M) contained in components (I) and (II).

[0173] The amount of component (IV) used is such that the total amount of transition metals contained in components (I) and (II) is 0.0001 mmol to 5 mmol, preferably 0.001 mmol to 0.5 mmol, and more preferably 0.01 mmol to 0.1 mmol per 1 g of component (IV).

[0174] An olefin polymerization catalyst can be obtained by contacting component (I), component (II), component (III), and component (IV) with each other by any of the contacting methods (1) to (3). Following the contacting step, a washing step may be carried out to remove unreacted materials and unwanted products, and then the solvent may be removed. In the washing step, the olefin polymerization catalyst is allowed to settle, and then the unnecessary supernatant liquid is removed, followed by adding new solvent and stirring to homogenize; the above stirring to homogenize is repeated; or washing is performed using a filter device. The solvent used in the washing step is a solvent that can be used in contact with components (I) to (IV). The solvent can also be changed during the washing step. The solvent removal step can be carried out by distillation at a pressure appropriate to the boiling point of the solvent, vaporizing the solvent with a dry inert gas stream, etc. The solvent is desirably removed 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 solvent removal step can be handled or stored as a powdered solid catalyst.

[0175] The olefin polymerization catalyst can also be obtained by the following method. Method (4): Components (I) and (II) are contacted with component (IV), which is a fine particle support, to remove the solvent, to form a solid catalyst component, which is then contacted with component (III), which is a co-catalyst, under polymerization conditions. Method (5): The co-catalyst component (III) is brought into contact with the fine particle support component (IV) to remove the solvent, forming a solid catalyst component, which is then brought into contact with the catalytically active components components (I) and (II) under polymerization conditions. In the above-mentioned methods (4) and (5), the component ratios, contact conditions, and solvent removal conditions can be the same as those described above.

[0176] Furthermore, a layered silicate can be used as both the promoter component (III) and the particulate carrier component (IV). A layered silicate is a silicate compound with a crystalline structure in which planes formed by ionic bonds or the like are stacked parallel to one another with weak bonding forces. Most layered silicates occur naturally, primarily as the main component of clay minerals, but these layered silicates are not limited to natural products and may also be synthetically produced. Among these, smectites, vermiculites, and micas such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite, and taeniolite are preferred.

[0177] Generally, natural products are often non-ion-exchangeable (non-swellable). In such cases, it is preferable to perform a treatment to impart ion-exchangeable (or swellable) properties to the product in order to impart the desired ion-exchangeable (or swellable) properties. Among such treatments, the following chemical treatments are particularly preferable. Here, chemical treatments can be used to refer to either surface treatments that remove impurities adhering to the surface or treatments that affect the crystalline structure and chemical composition of the layered silicate. Specific examples include (a) acid treatment using hydrochloric acid, sulfuric acid, etc., (b) alkali treatment using NaOH, KOH, NH3, etc., (c) salt treatment using salts consisting of a cation containing at least one atom selected from Groups 2 to 14 of the periodic table and at least one anion selected from the group consisting of halogen atoms or anions derived from inorganic acids, and (d) organic treatment using alcohols, hydrocarbon compounds, formamide, aniline, etc. These treatments may be carried out alone or in combination of two or more.

[0178] The particle properties of the layered silicate can be controlled by pulverization, granulation, sizing, fractionation, etc. at any time before, during, or after any of the steps. Any method suitable for the purpose can be used. In particular, examples of granulation methods include spray granulation, tumbling granulation, compression granulation, stirring granulation, briquetting, compaction, extrusion granulation, fluidized bed granulation, emulsion granulation, and submerged granulation. Of the above, particularly preferred granulation methods are spray granulation, tumbling granulation, and compression granulation.

[0179] The layered silicates described above can be used as they are, but they can also be used in combination with an organoaluminum compound such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, or diisobutylaluminum hydride, or an organoaluminum oxy compound containing an Al-O-Al bond.

[0180] In order to support the catalytically active components (I) and (II) on the layered silicate, the components (I) and (II) may be brought into contact with the layered silicate, or the components (I) and (II), the organoaluminum compound or the organoaluminum oxy-compound, and the layered silicate may be brought into contact with each other. The method for contacting the components is not particularly limited, and for example, the following methods can be optionally employed. Method (6): After component (I) and component (II) are contacted with the organoaluminum compound or organoaluminum oxy-compound, they are contacted with the layered silicate support. Method (7): After component (I) and component (II) are contacted with the layered silicate support, they are contacted with an organoaluminum compound or an organoaluminum oxy-compound. Method(8): The organoaluminum compound or organoaluminum oxy-compound is contacted with the layered silicate support, and then the resultant is contacted with component (I) and component (II).

[0181] Of these contact methods, methods (6) and (8) are preferred. In either contact method, the components are contacted with or without stirring in an inert atmosphere such as nitrogen or argon, generally in the presence of a liquid inert hydrocarbon, such as an aromatic hydrocarbon (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene, or ethylbenzene, or an aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as heptane, hexane, decane, dodecane, or cyclohexane. When component (I) and component (II) are supported on a layered silicate, the same conditions as those for the inorganic support can be used for the methods of supporting, washing with a solvent, and removing the solvent.

[0182] The proportions of the catalytically active components (I) and (II), the organoaluminum compound or organoaluminum oxy-compound, and the layered silicate support are not particularly limited, but the following ranges are preferred. The amount of component (I) and component (II) supported is such that the total amount of transition metal (M) contained in component (I) and component (II) is 0.0001 mmol to 5 mmol, preferably 0.001 mmol to 0.5 mmol, and more preferably 0.01 mmol to 0.1 mmol per 1 g of the layered silicate support. Furthermore, when an organoaluminum compound or an organoaluminum oxy-compound is used, the molar ratio (Al / M) of Al atoms contained in the organoaluminum compound or the organoaluminum oxy-compound to the total amount of the transition metal (M) contained in component (I) and component (II) is desirably in the range of 0.01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10.

[0183] IV. Prepolymerization of olefin polymerization catalysts The olefin polymerization catalyst thus obtained may be prepolymerized in the presence of an olefin, either inside a polymerization vessel or outside the polymerization vessel. Olefins refer to hydrocarbons containing at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, and divinylbenzene. However, there are no particular limitations on the type of olefin, and mixtures of these with other olefins may also be used. Ethylene and propylene are preferred, and ethylene is even more preferred.

[0184] The method of feeding the olefin during prepolymerization can be any method, such as a method of feeding the olefin to the reaction vessel at a constant rate or so as to maintain a constant pressure state, a combination thereof, or a method of changing the rate stepwise. The prepolymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours. The amount of prepolymerization is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, per part by weight of the polyolefin polymerization catalyst. After the prepolymerization is complete, the catalyst can be used as is depending on the type of use, but may be dried if necessary.

[0185] 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 the temperature is below this range, the reaction rate may decrease or the activation reaction may not proceed, whereas if the temperature exceeds this range, the prepolymerized polymer may dissolve, the particle properties may deteriorate due to an excessively fast prepolymerization rate, or the active sites may be deactivated due to a side reaction.

[0186] Prepolymerization can also be carried out in a liquid such as an organic solvent, and this is preferred. There are no particular restrictions on the concentration of the solid catalyst during prepolymerization, but it 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 components (I) and (II) progresses, resulting in a highly active catalyst.

[0187] Furthermore, during or after the contact of the olefin polymerization catalyst with the olefin, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania may be present.

[0188] After prepolymerization, the catalyst may be dried. There are no particular limitations on the drying method, and examples include drying under reduced pressure, drying by heating, and drying by passing a dry gas through the catalyst. These methods may be used alone or in combination of two or more. In the drying step, the catalyst may be stirred, vibrated, fluidized, or left to stand.

[0189] V. Polymerization of Olefins The olefin polymerization catalyst obtained by the present invention can be used for polymerizing an olefin alone or the olefin together with other comonomers. The polymerizable olefin preferably has about 2 to 20 carbon atoms, and specific examples thereof include ethylene, propylene, 1-butene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl-1,7-octadiene, cyclopentene, norbornene, ethylidenenorbornene, etc. Preferred are α-olefins having 2 to 8 carbon atoms.

[0190] In the case of copolymerization, an olefin other than the olefin serving as the main component can be selected from the above-mentioned olefins and used as the comonomer. When producing an ethylene copolymer, it is preferable to use an α-olefin having 3 to 8 carbon atoms, and more preferably an α-olefin having 4 to 6 carbon atoms, as the olefin comonomer.

[0191] Any polymerization method can be used as long as the catalyst components and each monomer are efficiently contacted. Specific examples include a slurry method using an inert solvent, a method using propylene as a solvent without substantially using an inert solvent, a solution polymerization method, and a gas-phase method in which each monomer is kept in a gaseous state without substantially using a liquid solvent. Continuous polymerization, batch polymerization, or prepolymerization methods can also be used. Among these, the slurry method is preferred. Also applicable is a method of multi-stage polymerization in which two or more stages are carried out in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature, etc. are different from each other. In the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as isobutane, hexane, heptane, pentane, cyclohexane, benzene, and toluene are used alone or in mixture as a polymerization solvent. The polymerization temperature is 0°C to 150°C, and hydrogen can be used supplementarily as a molecular weight modifier. The polymerization pressure is suitably 0 MPa to 200 MPa, preferably 0 MPa to 6 MPa. In the case of copolymerization, the ratio of the amounts of the monomers in the reaction system does not need to be constant over time, and it is convenient to supply the monomers at a constant mixing ratio, or it is also possible to change the mixing ratio of the supplied monomers over time. Also, it is possible to add any of the monomers in portions taking into account the copolymerization reaction ratio.

[0192] In general, when polymerizing an ethylene polymer, an antistatic agent such as Stadis or STATSAFE, manufactured by Innospec (distributor: Maruwa Bussan), can be used to suppress static adhesion of the polymer to the polymerization reactor. Antistatic agents such as Stadis and STATSAFE can also be diluted in an inert hydrocarbon medium and added to the polymerization reactor by a pump or the like. The addition method includes a method of adding it to an olefin polymerization catalyst in advance, a method of adding it to a polymerization reactor, etc. The amount added is preferably 0.1 ppm to 500 ppm, more preferably 1 ppm to 50 ppm, based on the solvent in the case of slurry polymerization, and preferably 1 ppm to 500 ppm, more preferably 10 ppm to 100 ppm, based on the amount of ethylene polymer produced per unit time in the case of a gas phase method.

[0193] The molecular weight of the resulting polymer can be adjusted by changing the polymerization temperature or by adding hydrogen to the polymerization reactor, but the 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 hydrogen-mediated chain transfer reaction, causing the polymer chain to lose its bond with the transition metal, preventing further increase in molecular weight. Therefore, increasing the amount of hydrogen added and increasing the hydrogen concentration in the reactor decreases the molecular weight, while decreasing the amount added and decreasing the hydrogen concentration increases the molecular weight. The ease with which this chain transfer reaction by hydrogen occurs varies with each individual olefin polymerization catalyst, and therefore the molecular weight can be controlled by the transition metal compound used. The olefin polymerization catalyst made from component (I) used in the present invention is prone to chain transfer reaction by hydrogen and is therefore suitable for producing low-molecular-weight polymers, while the olefin polymerization catalyst made from component (II) is unlikely to cause chain transfer reaction by hydrogen and is therefore suitable for producing high-molecular-weight polymers.

[0194] The molecular weight distribution of the produced polymer can be controlled by the types of the components (I) and (II) and the amounts of the components (I) and (II) contained in the olefin polymerization catalyst. The molecular weight distribution can be broadened by controlling the combination of component (I) and component (II) that increases the difference in the chain transfer reaction by hydrogen, and the component (I) and component (II) in the present invention are a suitable combination. Next, the shape of the molecular weight distribution, i.e., whether there is a large amount of low molecular weight polymer components or a large amount of high molecular weight polymer components, can be controlled by changing the amounts of component (I) and component (II).

[0195] The density of the resulting polymer can be controlled by the concentration of the comonomer used in copolymerization in the polymerization reactor. Increasing the comonomer feed rate and increasing the concentration in the polymerization reactor increases the amount of comonomer incorporated into the monomer chains in the polymer, inhibiting the polymer's crystallization and decreasing its density.

[0196] In polymerization, in addition to using a single reactor, multi-stage polymerization methods using multiple reactors are also used. In this method, reactors with the same or different reaction conditions are connected, and the polymer produced in the first reactor is fed, either with or without solvent, continuously or intermittently to the second reactor, where polymer production continues under the second reaction conditions. While there is no limit to the number of reactors, two or three reactors are preferably used. By varying various conditions, such as polymerization temperature, polymerization pressure, monomer concentration, comonomer concentration, and hydrogen concentration, between the first and subsequent reaction conditions, a mixture of polymers is produced in each reactor. Varying the hydrogen concentration can broaden the molecular weight distribution, and by combining hydrogen concentration with comonomer concentration, it is possible to produce polymers with different comonomer contents at different molecular weights. Furthermore, by varying the monomer concentration and polymerization temperature to change the amount of polymer produced in each reactor, it is possible to control the ratio of polymers produced in each reactor. In multi-stage polymerization, an olefin polymerization catalyst different from or the same as that in the first stage may be added in the second or subsequent stages, and a device for removing unreacted gas may be provided between reactors connected to each other.

[0197] A component for removing water, so-called a scavenger, may also be added to the polymerization system. Examples of such scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, the organoaluminum oxycompounds, modified organoaluminum compounds containing branched alkyl groups, organozinc compounds such as diethylzinc and dibutylzinc, organomagnesium compounds such as diethylmagnesium, dibutylmagnesium, and ethylbutylmagnesium, and Grignard compounds such as ethylmagnesium chloride and butylmagnesium chloride. Among these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferred, with triethylaluminum being particularly preferred.

[0198] VI. Physical properties of the obtained olefin copolymer By copolymerizing olefins using the olefin polymerization catalyst of the present invention, it is possible to produce an olefin copolymer having a sufficiently broad 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. The obtained olefin copolymer has high fluidity when melted, and high melt strength and elongational viscosity on the high strain side, and therefore has excellent moldability. In addition, it also has an excellent balance of rigidity, strength, and durability, and is therefore suitable for use as a plastic molding material. In particular, the ethylene copolymer obtained using the olefin polymerization catalyst of the present invention not only has high melt fluidity, melt strength, and elongational viscosity at high strain, resulting in excellent moldability, but also has an excellent balance of rigidity, strength, and durability, and is therefore suitable for use as a plastic molding material for high-density polyethylene (HDPE) grade applications. The olefin copolymer produced using the olefin polymerization catalyst of the present invention may be used in combination with another polymer. The olefin copolymer may also be used after being mixed with various additives other than the polymer, and then melt-kneaded.

[0199] In the present invention, an ethylene 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, i.e., MFR (190°C, 2.16 kg load) of the ethylene polymer obtained in the present invention is preferably 0.001 g / 10 min to 1000 g / 10 min, more preferably 0.005 g / 10 min to 200 g / 10 min, still more preferably 0.01 g / 10 min to 50 g / 10 min, and particularly preferably 0.02 g / 10 min to 5.0 g / 10 min.

[0200] (2) HLMFR (190°C, 21.6 kg load) The high load melt flow rate, i.e., HLMFR (190°C, 21.6 kg load) of the ethylene polymer obtained in the present invention is preferably 0.01 g / 10 min to 1000 g / 10 min, more preferably 0.1 g / 10 min to 500 g / 10 min, still more preferably 1.0 g / 10 min to 300 g / 10 min, and particularly preferably 2.0 g / 10 min to 100 g / 10 min.

[0201] (3) Density The density of the ethylene polymer obtained in the present invention is preferably 0.850 g / cm 3 ~0.980g / cm 3 and more preferably 0.935 g / cm 3 ~0.970g / cm 3 and more preferably 0.945 g / cm 3 ~0.965g / cm 3 is.

[0202] (4) Molecular weight distribution (Mw / Mn) The molecular weight distribution (Mw / Mn) of the ethylene polymer obtained in the present invention is preferably 6.0 or more and 60 or less, more preferably 8.0-50, still more preferably 10-40, and particularly preferably 15-25. 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 gel permeation chromatography (GPC).

[0203] (5) Ratio of comonomer content on the high molecular weight side to comonomer content on the low molecular weight side The ratio of the comonomer content on the high molecular weight side of the molecular weight distribution of the olefin polymer to the comonomer content on the low molecular weight side of the molecular weight distribution of the olefin polymer (comonomer content on the high molecular weight side / comonomer content on the low molecular weight side) is preferably 4 times or more, more preferably 8 times or more, and even more preferably 10 times or more. In the present invention, the ratio (high molecular weight comonomer content / low molecular weight comonomer content) is determined by the following experiment. [Method for determining the ratio (high molecular weight comonomer content / low molecular weight comonomer content)] An olefin polymerization catalyst containing component (I), component (III) and component (IV) but not containing component (II), and an olefin polymerization catalyst containing component (II), component (III) and component (IV) but not containing component (I) are prepared, and an olefin polymer is produced using each of these catalysts under the same polymerization conditions. Then, the number of branches contained in the low molecular weight copolymer obtained using a catalyst containing component (I) and the number of branches contained in the high molecular weight copolymer obtained using a catalyst containing component (II) are measured, and the ratio (high molecular weight comonomer content / low molecular weight comonomer content) is calculated. The obtained ratio value is specified as the ratio (high molecular weight comonomer content / low molecular weight comonomer content) of the olefin polymer obtained using the olefin polymerization catalyst containing components (I), (II), (III), and (IV).

[0204] (6) Melt tension (MT) The melt tension (MT) of the ethylene polymer obtained in the present invention, measured at a temperature of 190°C, is preferably 50 mN or more, more preferably 60 mN or more, and even more preferably 70 mN or more. Melt tension can be controlled by MFR and HLMFR. It can also be adjusted by molecular weight distribution. Reducing MFR and HLMFR increases melt tension, and broadening the molecular weight distribution also increases melt tension. Furthermore, melt tension is also affected by long chain branching; the greater the amount of long chain branching, the greater the melt tension. When the melt tension is within the above range, drawdown resistance is good and molding is easy.

[0205] (7) Tensile impact strength (TIS) The tensile impact strength (TIS) of the ethylene polymer obtained in the present invention is preferably 100 kJ / m 2 More preferably, 150 kJ / m 2 More preferably, it is 200 kJ / m or more. 2 That's all. In the present invention, the tensile impact strength (TIS) is measured in accordance with Method B of JIS K 7160-1996 using a test piece having the shape of ASTM D1822 Type-S. Tensile impact strength (TIS) can be controlled by the weight average molecular weight, molecular weight distribution, and density. Increasing the molecular weight, narrowing the molecular weight distribution, and decreasing the density will increase impact strength, but there is a trade-off with moldability.

[0206] (8) Environmental stress crack resistance The ethylene polymer obtained in the present invention has a time to rupture in a full notch creep test (FNCT) conducted in accordance with ISO 16770 of preferably 20 hours or more, more preferably 180 hours or more, and even more preferably 600 hours or more. Environmental stress crack resistance varies mainly with density. Increasing the comonomer content and decreasing the density increases environmental stress crack resistance (FNCT). The comonomer content in the low molecular weight side has little effect, but the comonomer content in the high molecular weight side has a large effect. Increasing the comonomer content in the high molecular weight side increases the FNCT time to rupture. Environmental stress crack resistance also increases with the content of high molecular weight components, and the more high molecular weight components are included, the longer the FNCT time to rupture. Therefore, polymers that have a longer time to rupture are those that contain comonomer in the high molecular weight side and have a sufficient amount of high molecular weight components. [Example]

[0207] 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, and the catalyst synthesis process and polymerization process were all carried out under a purified nitrogen atmosphere. The solvents used were dehydrated and purified using Molecular Sieve 4A (trade name, manufactured by Union Showa Co., Ltd.).

[0208] 1. Evaluation Method (1) MFR (190°C, 2.16 kg load) The MFR was measured in accordance with JIS K6760 under conditions of a temperature of 190°C and a load of 2.16 kg. (2) HLMFR (190°C, 21.6 kg load) The HLMFR was measured in accordance with JIS K6922-2:1997 under conditions of a temperature of 190°C and a load of 21.6 kg. (3) Density The density was measured in accordance with JIS K6922-1,2:1997.

[0209] (4) Molecular weight distribution (Mw / Mn) Gel permeation chromatography (GPC) was performed under the conditions shown below, and the number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by converting the retention volume into molecular weight, and the molecular weight distribution (Mw / Mn) was calculated. [GPC equipment, measurement conditions] Apparatus: Waters GPC (ALC / GPC 150C) Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm) Column: Showa Denko AD806M / S (3 columns) Mobile phase solvent: o-dichlorobenzene (ODCB) Measurement temperature: 140℃ Flow rate: 1.0ml / min Injection amount: 0.2ml [Sample preparation] The sample was dissolved in ODCB (containing 0.5 mg / mL of BHT) at 140° C. for about 1 hour to prepare a sample solution with a concentration of 1 mg / mL. [Conversion of retention volume to molecular weight] Conversion from retention volume to molecular weight was performed using a calibration curve prepared in advance using standard polystyrenes, all of which were manufactured by Tosoh Corporation and were the following brands: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, and A1000. A calibration curve is created by injecting 0.2 mL of a solution of each standard polystyrene dissolved in ODCB (containing 0.5 mg / mL BHT) so that the concentration is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximating using the least squares method. The viscosity equation [η] = K × Mα used to convert to molecular weight uses the following values. 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

[0210] (5) Measurement of comonomer content and terminal vinyl group content of polymer (NMR analysis) An ethylene polymer produced using a catalyst containing component (I) but not component (II), or a catalyst containing component (II) but not component (I), was vacuum dried at 80°C for 2 hours and then pressed at 190°C to form a pressed film. Approximately 200 mg of the pressed film and an ODCB-based mixed solvent were placed in an NMR sample tube and dissolved uniformly in a block heater at 150°C to prepare a sample solution. 13C-NMR and 1H-NMR were performed using this sample solution, and the comonomer content (calculated as the number of butyl branches) and terminal vinyl group content of the ethylene polymer were determined 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℃ [13C-NMR conditions] The number of butyl branches per 1000 carbon atoms (butyl branch number / 1000C) was calculated by dividing the peak area of ​​the butyl branch at 23.3 ppm obtained by 1H complete decoupling, a 45° pulse, an acquisition time of 2.5 seconds, a waiting time of 0.26 seconds, and accumulation of 10240 to 5120 times by the area of ​​the -CH2- main chain at 30 ppm. [1H-NMR conditions] The number of terminal vinyls per 1000 carbon atoms (number of terminal vinyls / 1000C) was calculated from the peak area derived from terminal H2C=C(H)-R at 4.8 to 6 ppm and the peak area derived from the -CH2- main chain at 1.3 ppm, obtained by solvent pre-saturation, 4.5° pulse, acquisition time of 1.8 seconds, waiting time of 0.2 seconds, and accumulation of 2048 to 1024 times.

[0211] (6) Molecular weight dependence of comonomer content in polymers (GPC-IR analysis) GPC-IR measurements were carried out on ethylene polymers produced using catalysts containing component (I) and component (II), and the correlation between the change in molecular weight and the number of short chain branches derived from the comonomer was observed. The GPC-IR was performed using the following equipment and conditions: [Device] Apparatus: GPC-IR manufactured by Ploymer Char. Detector: IR-6 Column: Showa Denko HT-806M (2 columns) Mobile phase solvent: o-dichlorobenzene (trimethylphenol 3.6 g / 18 L added as an antioxidant) Measurement temperature: 145℃ Flow rate: 1.0ml / min Injection volume: 20μL [Sample preparation] The sample was dissolved in a vial at a concentration of approximately 1 mg / ml and used for measurement. A calibration curve was created using standard polystyrene and converted to polyethylene using the Q factor. The Q factor used was the default value of -0.3649 in the Polymer Char software. The standard polystyrenes used were a sample set of Showdex Standard SM-105 (trade name, manufactured by Showa Denko K.K.), as well as n-eicosane and n-tetracontane. The molecular weights of n-eicosane and n-tetracontane were converted to polystyrene using the Q factor.

[0212] (7) Melt tension (MT) It is determined by measuring the stress when a molten ethylene polymer is stretched at a constant speed, and is measured under the following conditions. [Measurement conditions] Model used: Toyo Seiki Co., Ltd., Capillograph 1B Nozzle diameter: 2.095 mm Nozzle length: 8.0 mm Inflow angle: 180°(flat) Extrusion speed: 15mm / min Take-up speed: 6.5m / min Measurement temperature: 190℃

[0213] (8) Tensile impact strength (TIS) [How to prepare samples for tensile impact strength tests] The sample was placed in a 1 mm thick heat press mold and preheated for 5 minutes at a surface temperature of 230 °C. The sample was then melted and degassed by repeatedly applying pressure and depressurizing the pressure. The mold was then pressurized to 4.9 MPa and held for 5 minutes. The mold was then gradually cooled at a rate of 10 °C / min while still under pressure at 4.9 MPa. Once the temperature had dropped to near room temperature, the molded plate was removed. The resulting plate was conditioned for at least 48 hours at a temperature of 23 ± 2 °C and a humidity of 50 ± 5 °C. Test specimens conforming to ASTM D1822 Type-S were punched out of the conditioned press plate to prepare samples for tensile impact strength testing. [Tensile Impact Strength Test Conditions (TIS)] Using the above test specimens, the tensile impact strength was measured in accordance with Method B of JIS K 7160-1996. Note that the only difference from JIS K 7160-1996 was the shape of the test specimen. Other measurement conditions were the same as those in JIS K 7160-1996.

[0214] (9) Environmental stress cracking resistance (FNCT) A full notch creep test (FNCT) was performed in accordance with ISO 16770. A specimen was prepared by making a 1 mm notch with a razor blade around the entire periphery of a 6 mm x 6 mm x 11 mm square pillar, giving it a cross section of 4 mm x 4 mm. A tensile stress equivalent to 3.7 MPa was applied to the specimen in pure water at 80°C, and the time until the specimen broke was measured and recorded as the FNCT time to break.

[0215] 2. Synthesis examples 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. 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.

[0216] [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 A 500 ml flask was charged with 10.00 g (0.09419 mol) of o-xylene and 94.20 ml (0.9487 mol) of concentrated hydrochloric acid and cooled to 0°C. To this was added 8.55 g (0.0377 mol) of 1-butyl-3-methylimidazolium tetrafluoroborate and 8.56 g (0.283 mol) of paraformaldehyde, followed by stirring at 70°C for 12 hours. An additional 94.20 ml (0.9487 mol) of concentrated hydrochloric acid and 2.85 g (0.0942 mol) of paraformaldehyde were added, followed by stirring at 70°C for an additional 12 hours. The reaction mixture was concentrated by evaporation under reduced pressure, 200 ml of distilled water was added, and the mixture was extracted three times with 200 ml of dichloromethane. The resulting organic phase was washed with 200 ml of distilled water and dried over anhydrous sodium sulfate. The sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column (petroleum ether) to obtain 18.00 g (yield 94%) of a white powder of 3,4-dimethyl-α,α'-dichloro-o-xylene.

[0217] (2-2) Synthesis of α,α'-bis-(1-indenyl)-3,4-dimethyl-o-xylene A 500 ml flask was charged with 17.16 g (0.1477 mol) of indene and 200 ml of THF and cooled to -78 °C. 55.14 ml (0.1379 mol) of a 2.5 M n-butyllithium / n-hexane solution was added dropwise, and the mixture was allowed to warm to room temperature and stirred for 2 hours. The mixture was again cooled to -78 °C, and a solution of 10.00 g (0.04923 mol) of 3,4-dimethyl-α,α'-dichloro-o-xylene in 50 ml of THF was added dropwise. The mixture was allowed to warm to room temperature and stirred overnight. The reaction mixture was slowly poured into 200 ml of distilled water and extracted three times with 250 ml of dichloromethane. The resulting organic phase was washed with 120 ml of saturated brine and dried over anhydrous sodium sulfate. The sodium sulfate was filtered off, the solvent was evaporated under reduced pressure, and the residue was purified with a silica gel column (petroleum ether / ethyl acetate=10 / 1) to obtain 12.00 g (yield 67%) of a yellow oil of α,α'-bis-(1-indenyl)-3,4-dimethyl-o-xylene.

[0218] (2-3) Synthesis of {3,4-dimethyl-o-xylene-α,α'-bis-(η5-1-indenyl)-zirconium} dichloride A 200 ml flask was charged with 1.99 g (5.49 mmol) of α,α'-bis-(1-indenyl)-3,4-dimethyl-o-xylene and 60 ml of THF and cooled to -78°C. 7.20 ml (11.4 mmol) of a 1.58 M n-butyllithium / n-hexane solution was added dropwise, and the mixture was allowed to warm to room temperature and stirred for 3 hours. A separately prepared solution of 1.54 g (6.61 mmol) of zirconium tetrachloride in 10 ml of n-hexane and 40 ml of THF was added at 0°C and stirred overnight while gradually warming to room temperature. The solvent was removed from the reaction mixture by distillation under reduced pressure, yielding a yellow powder. 35 ml of toluene was added to this powder at room temperature and stirred for 30 minutes. Insoluble matter was removed by filtration, and the solvent was removed from the filtrate by distillation under reduced pressure, yielding a yellow powder again. The resulting yellow powder was recrystallized from a mixed solvent of dichloromethane / n-hexane to obtain 0.284 g (yield 10%) of a yellow powder of {3,4-dimethyl-o-xylene-α,α'-bis-(η5-1-indenyl)-zirconium} dichloride. 1H-NMR value (CDCl3): 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).

[0219] [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.

[0220] [Synthesis Example 4] Bis(n-butylcyclopentadienyl)zirconium dichloride (hereinafter abbreviated as metallocene I-4) was obtained from Fujifilm Wako Pure Chemical Industries, Ltd.

[0221] [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 formula (2-1). Metallocene II-1 was synthesized by synthesizing a ligand according to the procedure described in Synthesis Example 1 of Japanese Patent Application No. 2011-008562, using zirconium tetrachloride instead of hafnium tetrachloride.

[0222] [Synthesis Example 6] Synthesis of racemic dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride (hereinafter referred to as metallocene II-2): Metallocene II-2 was synthesized according to the procedure described in Organometallics, 1994, vol. 13, pp. 954-963.

[0223] [Synthesis Example 7] Synthesis of {diphenylmethylene(3-methyl-1-cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)}zirconium dichloride (hereinafter referred to as metallocene II-3): Metallocene II-3 was synthesized according to the procedure described in Manufacturing Example 2 of US 2015 / 0299352 A1.

[0224] 3. Catalyst preparation and production of ethylene polymers [Example 1] (1) Preparation of solid catalyst Component (IV) was prepared in advance by adding 38 ml of toluene to 3.8 g of silica gel, which was prepared by calcining uncalcined Grace Sylopol 2212 at 400°C for 7 hours, and forming a slurry at 40°C. Separately from the above process, 28 mg (58 μmol) of metallocene I-1 as component (I) and 32 mg (38 μmol) of metallocene II-1 as component (II) were weighed in a container, to which 25 ml of toluene and 10 ml (30 mmol of aluminum) of methylaluminoxane toluene solution as component (III) (purchased from Albemarle; MAO concentration 20 wt%) were added, followed by stirring at room temperature for 1 hour. The total amount of metallocene I-1 and metallocene II-1 per 1 g of silica gel was 25 μmol / g. This solution was added to a toluene slurry of silica gel, which was component (IV). After stirring at 40°C for 1 hour, the solvent was removed under reduced pressure to obtain a pink, smooth solid catalyst (MIX-1).

[0225] (2) Ethylene / hexene copolymerization Ethylene-1-hexene copolymer was produced using the solid catalyst (MIX-1) obtained in (1) above. Specifically, 1.0 mmol of triisobutylaluminum, 2 ml of 1-hexene, 1 ml of a reactor fouling inhibitor (Innospec's Statsafe 6000 product) diluted to 2 vol% with hexane, and 800 ml of purified isobutane were placed in a 2-liter stainless steel autoclave equipped with stirring and temperature control under nitrogen, and the mixture was heated to 70°C with stirring. Next, 15 ml (0.67 mmol) of hydrogen was introduced, followed by ethylene until the partial pressure reached 1 MPa. Subsequently, 50 mg of the solid catalyst (MIX-1) was introduced under nitrogen pressure, and polymerization was carried out for 60 minutes. During polymerization, the temperature was controlled to maintain 70°C, and ethylene was continuously supplied to maintain a constant total pressure. 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 polymerization was 0.09 mol%, and at the end of polymerization it remained at 0.1 mol%. Furthermore, 2 ml of 1-hexene was added during the polymerization, which was 0.9 wt% of the polyethylene produced. As a result of the polymerization, 142 g of free-flowing polyethylene was produced. The polymerization results are summarized in Table 2. The GPC-IR results of the obtained polyethylene are shown in Figure 1. It can be seen that by combining metallocene I-1 and metallocene II-1, the molecular weight distribution is broadened and the comonomer is preferentially introduced into the high molecular weight region.

[0226] [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 per 1 g of silica gel instead of using metallocene I-1 and metallocene II-1, and ethylene / hexene copolymerization was carried out in the same manner as in Example 1. 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 per 1 g of silica gel instead of using metallocene I-1 and metallocene II-1, and ethylene / hexene copolymerization was carried out in the same manner as in Example 1. The results are summarized in Table 2.

[0227] [Example 2] (1) Preparation of solid catalyst A solid catalyst MIX-2 was obtained in the same manner as in Example 1, except that 30 mg (58 μmol) of metallocene I-2 was used as component (I) instead of metallocene I-1. (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 polymerization was 0.08 mol%, and was maintained at 0.1 mol% at the end of polymerization. 2 ml of 1-hexene was added during the polymerization, which was 1.0 wt% of the polyethylene produced. As a result of the polymerization, 139 g of free-flowing polyethylene was produced. The polymerization results are summarized in Table 2.

[0228] [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 per 1 g of silica gel instead of metallocene I-1 and metallocene II-1, and ethylene / hexene copolymerization was carried out in the same manner as in Example 1. The results are summarized in Table 2.

[0229] [Example 3] (1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1, except that 42 mg (76 μmol) of metallocene I-3 was used instead of metallocene I-1 as component (I) and the amount of metallocene II-1 used as component (II) was 16 mg (19 μmol), thereby obtaining 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 polymerization was 0.12 mol%, while at the end of polymerization it was 0.06 mol%. Furthermore, 1 ml of 1-hexene was added during the polymerization, which was 0.5 wt% of the polyethylene produced. As a result of the polymerization, 134 g of free-flowing polyethylene was produced. The polymerization results are summarized in Table 2.

[0230] [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 per 1 g of silica gel instead of metallocene I-1 and metallocene II-1, and ethylene / hexene copolymerization was carried out in the same manner as in Example 1. The results are summarized in Table 2.

[0231] [Example 4] (1) Preparation of solid catalyst A solid catalyst MIX-4 was prepared in the same manner as in Example 1, except that 24 mg (38 μmol) of metallocene II-2 was used as component (II) instead of metallocene II-1. (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 polymerization was 0.07 mol%, while at the end of polymerization it was 0.06 mol%. Furthermore, 2 ml of 1-hexene was added during the polymerization, which was 1.1 wt% of the polyethylene produced. 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 copolymer properties The resulting ethylene / hexene copolymer was subjected to measurements of molecular weight distribution, MT, TIS, and FNCT. The results are summarized in Table 4. The results of GPC-IR of the resulting polyethylene are shown in Figure 2.

[0232] [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 per 1 g of silica gel instead of metallocene I-1 and metallocene II-1, and ethylene / hexene copolymerization was carried out in the same manner as in Example 1. The results are summarized in Table 2.

[0233] [Example 5] (1) Preparation of solid catalyst A solid catalyst MIX-5 was prepared in the same manner as in Example 1, except that 26 mg (38 μmol) of metallocene II-3 was used as component (II) instead of metallocene II-1. (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 polymerization was 0.09 mol%, while at the end of polymerization it was 0.08 mol%. Furthermore, 2 ml of 1-hexene was added during the polymerization, which was 0.9 wt% of the polyethylene produced. As a result of the polymerization, 145 g of free-flowing polyethylene was produced. The polymerization results are summarized in Table 2.

[0234] [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 per 1 g of silica gel instead of metallocene I-1 and metallocene II-1. Ethylene / hexene copolymerization was then carried out in the same manner as in Example 1, except that the amount of hydrogen was changed from 15 ml (0.67 mmol) to 50 ml (2.2 mmol). The results are summarized in Table 2. When polymerization was performed using SII-3 at the same hydrogen concentration as in Example 1, polyethylene that did not flow was obtained, so the hydrogen concentration was increased.

[0235] [Example 6] (1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1, except that the amount of metallocene I-1 used as component (I) was 34 mg (68 μmol) and the amount of metallocene II-1 used as component (II) was 19 mg (23 μmol), thereby obtaining 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 30 mL (1.3 mmol) of hydrogen was used. The molar ratio of hydrogen to ethylene in the gas phase of the autoclave before the start of polymerization was 0.18 mol%, while at the end of polymerization it was 0.13 mol%. Furthermore, 1 mL of 1-hexene was added during the polymerization, which was 0.9 wt% of the polyethylene produced. The polymerization resulted in the production of 78 g of free-flowing polyethylene. (3) Evaluation of copolymer properties The obtained ethylene / hexene copolymer was subjected to measurements of molecular weight distribution, MT, TIS, and FNCT. The results are summarized in Table 4.

[0236] [Example 7] (1) Preparation of solid catalyst A solid catalyst was prepared in the same manner as in Example 1, except that the amount of metallocene I-1 used as component (I) was 32 mg (65 μmol) and the amount of metallocene II-1 used as component (II) was 19 mg (30 μmol), thereby obtaining solid catalyst MIX-7. (2) Ethylene / hexene copolymerization Next, ethylene / hexene copolymerization was carried out in the same manner as in Example 1, except that 42 mg of MIX-7 was used, 25 ml (1.1 mmol) of hydrogen was added, and polymerization was carried out at 90°C for 0.9 hours. The molar ratio of hydrogen to ethylene in the gas phase of the autoclave before the start of polymerization was 0.14 mol%, while at the end of polymerization it was 0.09 mol%. Furthermore, 2 ml of 1-hexene was added during the polymerization, which was 0.9 wt% of the polyethylene produced. The polymerization resulted in 150 g of free-flowing polyethylene. (3) Evaluation of copolymer properties The resulting ethylene / hexene copolymer was subjected to measurements of molecular weight distribution, MT, TIS, and FNCT. The results are summarized in Table 4. The results of GPC-IR of the resulting polyethylene are shown in Figure 3.

[0237] Comparative Example 6 (1) Preparation of solid catalyst A solid catalyst MIX-8 was prepared in the same manner as in Example 1, except that 23 mg (58 μmol) of metallocene I-4 was used instead of metallocene I-1 as component (I) and 24 mg (38 μmol) of metallocene II-2 was used instead of metallocene II-1 as component (II). (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-8 was used, the amount of hydrogen was 38 mL (1.7 mmol), and the amount of 1-hexene was 1 mL. The molar ratio of hydrogen to ethylene in the gas phase of the autoclave before the start of polymerization was 0.19 mol%, while at the end of polymerization it was 0.11 mol%. Furthermore, 1 mL of 1-hexene was added during the polymerization, which was 0.5 wt% of the polyethylene produced. The polymerization resulted in the production of 130 g of free-flowing polyethylene. (3) Evaluation of copolymer properties The obtained ethylene / hexene copolymer was subjected to measurements of molecular weight distribution, MT, TIS, and FNCT. The results are summarized in Table 4.

[0238] Comparative Example 7 The physical properties of Evolue H SP6505 (trade name, manufactured by Prime Polymer Co., Ltd., a medium- to high-density polyethylene obtained by a slurry-type multistage polymerization process using a metallocene catalyst) were measured, and the results are summarized in Table 4.

[0239] [Comparative Example 8] The physical properties of Novatec HD HB431 (Japan Polyethylene Corporation, high density polyethylene) were measured and the results are summarized in Table 4.

[0240] [Reference example] The following examples were carried out to demonstrate the characteristics of the transition metal compounds used in the examples. The combination of metallocene I-1 and metallocene II-1 resulted in a high ratio of butyl branching, as high as 13 times. [Reference example 1] Ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1, except that solid catalyst SI-1 was used and 6 ml of 1-hexene was used. The number of butyl branches and the number of terminal vinyl groups 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 solid catalyst SII-1 was used and 6 ml of 1-hexene was used. The number of butyl branches and the number of terminal vinyl groups were determined by NMR analysis of the obtained polyethylene. The results are summarized in Table 3.

[0241] [Reference example 3] Ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 1, except that solid catalyst SI-2 was used and 6 ml of 1-hexene was used. The number of butyl branches and the number of terminal vinyl groups 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 solid catalyst SI-3 was used and 6 ml of 1-hexene was used. The number of butyl branches and the number of terminal vinyl groups 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 solid catalyst SII-2 was used and the hydrogen and 1-hexene were changed to 75 ml (3.3 mmol) and 6 ml, respectively. The number of butyl branches and the number of terminal vinyl groups were determined by NMR analysis of the resulting 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 solid catalyst SII-3 was used and the hydrogen and 1-hexene were changed to 70 ml (3.1 mmol) and 6 ml, respectively. The number of butyl branches and the number of terminal vinyl groups were determined by NMR analysis of the resulting polyethylene. The results are summarized in Table 3.

[0242] [Table 2]

[0243] (*1) Polymerization activity unit: g / g / h / MPa (ethylene partial pressure) The polymerization activity is the amount of polymer produced (unit: g) per g of solid catalyst, per hour of polymerization time, and per 1 MPa of ethylene partial pressure. (*2) Average value (unit: mol%) determined by gas analysis of the gas phase of the reactor during polymerization.

[0244] [Table 3]

[0245] [Table 4]

[0246] 4. Discussion From Comparative Examples 1a and 1b in Table 2, it can be seen that when component (I) or component (II) is used alone as the catalytically active component, the molecular weight distribution of the resulting ethylene polymer is narrow. In contrast, it can be seen that the molecular weight distribution of the resulting ethylene polymer is broadened by combining metallocene I-1 and metallocene II-1 in Example 1. Similarly, it can be seen that the molecular weight distribution is broadened in Example 2 compared to Comparative Example 2a and Comparative Example 1b, in Example 3 compared to Comparative Example 3a and Comparative Example 1b, in Example 4 compared to Comparative Example 1a and Comparative Example 4b, and in Example 5 compared to Comparative Example 1a and Comparative Example 5b.

[0247] Figure 1 shows the results of the GPC-IR analysis of Example 1. SCB (Short Chain Branch) refers to the number of short chain branches determined from the intensity of CH3 groups detected by IR analysis, and in this example, it indicates the number of branched chains with four carbon atoms formed by copolymerizing the comonomer hexene. Note that the large SCB in the region where LogM is less than 4 is due to an error caused by the detection of CH3 groups at the ends of the polyethylene molecules, and does not mean that there is actually a large amount of SCB. In Figure 1, it is believed that the low-molecular-weight polyethylene with a peak at logM 4.5 is produced from the catalytic reaction of the solid catalyst (SI-1) containing metallocene I-1, component (I), and the high-molecular-weight polyethylene with a peak at logM 5.9 is produced from the catalytic reaction of the solid catalyst (SII-1) containing metallocene II-1, component (II). When the SCB of each peak is read, the SCB derived from metallocene I-1 is nearly 0, and the SCB derived from metallocene II-1 is 2.5. If we assume that the SCB derived from metallocene I-1 is at most 0.1, the ratio of the hexene content (SCB ratio) between the high molecular weight region and the low molecular weight region of the polyethylene obtained in Example 1 is a high value of 2.5 / 0.1 = 25 times, indicating that by combining component (I) and component (II), it is possible to introduce comonomers to a high degree into the high molecular weight region of the olefin polymer. Examples of similar analytical results are shown in Figures 2 and 3 for Examples 4 and 7, respectively. It can be seen that in both cases, comonomers were introduced to a high degree into the high molecular weight region.

[0248] The number of butyl branches in Table 3 refers to the number of branched chains with four carbon atoms produced by copolymerization of the comonomer hexene. When ethylene / 1-hexene copolymerization was carried out using either metallocene II-1, used as component (II) in Example 1, or metallocene I-1, used as component (I), alone under the same polymerization conditions, the copolymer derived from metallocene II-1 had a butyl branch number of 5.1, while the copolymer derived from metallocene I-1 had a butyl branch number of 0.4 / 1000C. That is, the ratio (comonomer content on the high molecular weight side / comonomer content on the low molecular weight side) 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 broad and the comonomer is preferentially introduced into the high molecular weight side. As such, the characteristics of component (II) and component (I) are similarly shown in Reference Examples 3 to 6 in Table 3, and it can be seen that the combination of component (I) and component (II) of the present application is a combination that allows for a high degree of comonomer introduction into the high molecular weight side. Table 4 compares the physical properties of the resulting polyethylene. Comparative Example 6 uses an unbridged metallocene as component (I), and although it has the same molecular weight distribution and nearly the same HLMFR as Example 4, it is low in strength, FNCT, and MT. Comparative Example 7 is polyethylene obtained by two-stage polymerization using a metallocene catalyst, and while it has high strength and a sufficiently high FNCT, its low MT results in poor moldability. Comparative Example 8 is a commercially available HDPE grade, and Examples 4, 6, and 7 are superior in terms of high strength, FNCT, and MT. [Industrial Applicability]

[0249] By copolymerizing olefins using the olefin polymerization catalyst component or olefin polymerization catalyst of the present invention, it is possible to produce an olefin polymer having a sufficiently broad molecular weight distribution, with the distribution spreading 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. Therefore, the present invention can be used to produce an olefin copolymer having excellent moldability and an excellent balance between rigidity, strength, and durability, and can be suitably used in particular to produce an ethylene copolymer suitable for high density polyethylene (HDPE) grade applications.

Claims

1. A catalyst component for olefin polymerization, comprising the following components (I) and (II): [Component (I)] A transition metal compound represented by the following formula (1): 【Chemical 1】 [In the formula, M １ indicates a transition metal of Group 4 of the periodic table. L １ and L ２ represents a ligand containing a cyclopentadienyl structure, and M １ It is coordinated to. X １ and X ２ are each independently M １ and represents 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon-substituted amino group having 1 to 20 carbon atoms, which is bonded to the above. J １ and J ２ indicates a carbon atom. A １ and A ２ are J １ and L １ , J ２ and L ２ and is selected from the following group: -CR ３ ２ -, -SiR ３ ２ -, -NR ３ -, -PR ３ -, -O-, -S-, [where R ３ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and two R ３ may be bonded to form a cyclic structure], R １ and R ２ R each independently represents a hydrogen 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 and containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms. １ and R ２ are combined together to form J １ and J. ２ may form a cyclic structure together with [Component (II)] A transition metal compound represented by the following formula (2): Formula (2): A ３ ｑ L ３ L ３’ M ３ X ３ X ３’ [In the formula, M ３ indicates a transition metal of Group 4 of the periodic table. L ３ and L ３’ each independently represents a ligand containing a cyclopentadienyl structure, M ３ The ligand containing a cyclopentadienyl structure may be substituted with 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 and containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms. ３ or L ３’ When adjacent substituents are present on the aryl group, they may be bonded to form a ring structure. X ３ and X ３’ are each independently M ３ and represents 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon-substituted amino group having 1 to 20 carbon atoms, which is bonded to the above. A ３ Is, L ３ and L ３’ and is an alkylene group having 1 to 20 carbon atoms which may have a substituent, a silylene group which may have a substituent, or a germylene group which may have a substituent, and may be present or absent. When present, ３ and L ３’ There is a bridge structure between them. q is 0 or 1, and A ３ Indicates the number of

2. The component (I) is a compound represented by the formula (1), １ , R ２ , J １ and J. ２ 2. The catalyst component for olefin polymerization according to claim 1, wherein the ring structure is formed by the ring structure.

3. 3. The catalyst component for olefin polymerization according to claim 2, wherein the component (I) is a transition metal compound represented by any one of the following formulas (1-1) to (1-5): 【Chemistry 2-1】 【Chemistry 2-2】 【Chemistry 2-3】 【Chemistry 2-4】 【Chemistry 2-5】 [In the formula, M １ , L １ , L ２ , X １ , X ２ , J １ , J ２ , A １ and A ２ is the same as the above formula (1). R ４ represents a substituent present on the 6-membered ring, which may or may not be present, and when present, each independently represents a halogen atom, a hydrocarbon group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 9 carbon atoms, a hydrocarbon group having 3 to 9 carbon atoms containing an oxygen atom, a sulfur atom or a nitrogen atom, a hydrocarbon-substituted silyl group having 1 to 9 carbon atoms, or an amino group optionally substituted with a hydrocarbon group having 1 to 9 carbon atoms. ４ is the R ４ A bridge structure may be formed within the six-membered ring in which R ４ When there are two or more R ４ may form a fused ring sharing some of the constituent atoms of the six-membered ring in which the group is present, or the fused ring may have a substituent. n is R present on the 6-membered ring ４ represents the number of digits, ranging from 0 to 4.

4. The component (II) is a compound represented by the formula (2), in which q is 1 and L ３ and L ３’ and (b) each have an indenyl skeleton; one of the ligands has a cyclopentadienyl skeleton and the other has a fluorenyl skeleton; or both of the ligands have fluorenyl skeletons.

5. The component (II) is a compound represented by the formula (2), in which q is 1 and L ３ and L ３’ are all ligands having an indenyl skeleton, and L ３ and L ３’ The olefin polymerization catalyst component according to claim 4, wherein at least one of the ligands having an indenyl skeleton is a transition metal compound having, at the 2-position of the indenyl skeleton, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an optionally substituted furyl group, or an optionally substituted thienyl group.

6. The component (II) is a compound represented by the formula (2), in which q is 1 and L ３ and L ３’ are all ligands having an indenyl skeleton, and L ３ and L ３’ the ligand having an indenyl skeleton of at least one of the above is a transition metal compound having an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an optionally substituted furyl group, or an optionally substituted thienyl group at the 2-position of the indenyl skeleton, and further having an optionally substituted aryl group at the 4-position of the indenyl skeleton.

7. 7. The catalyst component for olefin polymerization according to claim 6, wherein the component (II) is a transition metal compound represented by the following formula (2-1): 【Chemistry 3】 [In the formula, M ３ represents a titanium atom, a zirconium atom, or a hafnium atom. X ３ and X ３’ are X in the formula (2), respectively. ３ and X ３’ is the same as Y represents a carbon atom, a silicon atom, or a germanium atom. R １１ and R ２１ R each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a furyl group which may have a substituent, or a thienyl group which may have a substituent. １１ and R ２１ At least one of the groups is either an optionally substituted furyl group or an optionally substituted thienyl group. 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 R each independently represents 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, an alkyl group having 1 to 6 carbon atoms and having a trialkylsilyl 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 heterocyclic group forming a 5- or 6-membered ring which may have a substituent. １２ ~R １９ and R ２２ ~R ２９ Adjacent groups among these may be bonded to each other to form a 6- or 7-membered ring, and the 6- or 7-membered ring may contain an unsaturated bond. R ３１ and R ３２ R each independently represents 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, an alkyl group having 1 to 6 carbon atoms and having a trialkylsilyl 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 heterocyclic group forming a 5- or 6-membered ring which may have a substituent. ３１ and R ３２ may form a 4- to 7-membered ring together with Y, and R ３１ and R ３２ When at least one of R ３１ and R ３２ and Y are 4 to 7 membered rings ３１ and R ３２ may form a fused ring sharing some of the constituent atoms of the cyclic structure of

8. An olefin polymerization catalyst comprising the following components (I), (II), (III) and (IV): [Component (I)] A transition metal compound represented by the following formula (1): 【Chemistry 4】 [In the formula, M １ indicates a transition metal of Group 4 of the periodic table. L １ and L ２ represents a ligand containing a cyclopentadienyl structure, and M １ It is coordinated to. X １ and X ２ are each independently M １ and represents 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon-substituted amino group having 1 to 20 carbon atoms, which is bonded to the above. J １ and J ２ indicates a carbon atom. A １ and A ２ are J １ and L １ , J ２ and L ２ and is selected from the following group: -CR ３ ２ -, -SiR ３ ２ -, -NR ３ -, -PR ３ -, -O-, -S-, [where R ３ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and two R ３ may be bonded to form a cyclic structure], R １ and R ２ R each independently represents a hydrogen 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 and containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms. １ and R ２ are combined together to form J １ and J. ２ may form a cyclic structure together with [Component (II)] A transition metal compound represented by the following formula (2): Formula (2): A ３ ｑ L ３ L ３’ M ３ X ３ X ３’ [In the formula, M ３ indicates a transition metal of Group 4 of the periodic table. L ３ and L ３’ each independently represents a ligand containing a cyclopentadienyl structure, M ３ The ligand containing a cyclopentadienyl structure may be substituted with 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 and containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms. ３ or L ３’ When adjacent substituents are present on the aryl group, they may be bonded to form a ring structure. X ３ and X ３’ are each independently M ３ and represents 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon-substituted amino group having 1 to 20 carbon atoms, which is bonded to the above. A ３ Is, L ３ and L ３’ and is an alkylene group having 1 to 20 carbon atoms which may have a substituent, a silylene group which may have a substituent, or a germylene group which may have a substituent, and may be present or absent. When present, ３ and L ３’ There is a bridge structure between them. q is 0 or 1, and A ３ Indicates the number of [Component (III)] A compound that reacts with the transition metal compounds of component (I) and component (II) to generate a cationic compound. [Component (IV)] Microparticle carrier

9. An olefin polymerization catalyst produced by mixing the following components (I), (II), (III) and (IV): [Component (I)] A transition metal compound represented by the following formula (1): 【Chemistry 5】 [In the formula, M １ indicates a transition metal of Group 4 of the periodic table. L １ and L ２ represents a ligand containing a cyclopentadienyl structure, and M １ It is coordinated to. X １ and X ２ are each independently M １ and represents 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon-substituted amino group having 1 to 20 carbon atoms, which is bonded to the above. J １ and J ２ indicates a carbon atom. A １ and A ２ are J １ and L １ , J ２ and L ２ and is selected from the following group: -CR ３ ２ -, -SiR ３ ２ -, -NR ３ -, -PR ３ -, -O-, -S-, [where R ３ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and two R ３ may be bonded to form a cyclic structure], R １ and R ２ R each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms. １ and R ２ are combined together to form J １ and J. ２ may form a cyclic structure together with [Component (II)] A transition metal compound represented by the following formula (2): Formula (2): A ３ ｑ L ３ L ３’ M ３ X ３ X ３’ [In the formula, M ３ indicates a transition metal of Group 4 of the periodic table. L ３ and L ３’ each independently represents a ligand containing a cyclopentadienyl structure, M ３ The ligand containing a cyclopentadienyl structure may be substituted with 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 and containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms and containing an oxygen atom, a sulfur atom, or a nitrogen atom, or a hydrocarbon-substituted silyl group having 1 to 20 carbon atoms. ３ or L ３’ When adjacent substituents are present on the aryl group, they may be bonded to form a ring structure. X ３ and X ３’ are each independently M ３ and represents 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 containing an oxygen atom or a nitrogen atom, or a hydrocarbon-substituted amino group having 1 to 20 carbon atoms, which is bonded to the above. A ３ Is, L ３ and L ３’ and is an alkylene group having 1 to 20 carbon atoms which may have a substituent, a silylene group which may have a substituent, or a germylene group which may have a substituent, and may be present or absent. When present, ３ and L ３’ There is a bridge structure between them. q is 0 or 1, and A ３ Indicates the number of [Component (III)] A compound that reacts with the transition metal compounds of component (I) and component (II) to generate a cationic compound. [Component (IV)] Microparticle carrier

10. A method for producing an ethylene polymer, comprising copolymerizing ethylene and an α-olefin selected from the group consisting of α-olefins other than ethylene, using the olefin polymerization catalyst according to claim 8 or 9.

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