Catalyst for olefin polymerization and method for producing ethylene polymers

Abstract

To provide a catalyst for olefinic polymerization that makes it possible to produce an ethylenic polymer having moldability, strength and durability in a balanced manner.SOLUTION: A catalyst for olefinic polymerization contains a component (A): a specific uncrosslinked metallocene compound, a component (B): a specific crosslinked metallocene compound, a component (C): a compound that makes the component (A) and the component (B) cationic compounds, and a component (D): particulate carrier.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an olefin polymerization catalyst useful for producing olefin polymers and copolymers, and to a method for producing ethylene-based polymers using the olefin polymerization catalyst. [Background technology]

[0002] Olefin polymers such as polyethylene and polypropylene are widely used as plastic molding materials. Olefin polymers used as molding materials require moldability such as fluidity in the molten state, melt tension, and extensional viscosity, as well as physical properties suitable for the application of the molded product, such as hardness, rigidity, impact strength, heat resistance, durability, and transparency after molding. In this context, polyolefins produced using metallocene catalysts for olefin polymerization have been increasing in use in recent years due to their high uniformity of polymer molecular structure, such as molecular weight distribution and copolymer composition distribution, and their excellent mechanical properties, including impact strength and long lifespan. However, although metallocene-based polyolefins have excellent mechanical properties, their narrow molecular weight distribution results in inferiority in important properties for polyolefin molding, such as melt tension and melt flowability, and they have not met sufficient performance requirements in terms of molding.

[0003] As a method for improving the moldability of metallocene polyolefins, Patent Document 1 discloses a catalyst that combines multiple crosslinked metallocene complexes of a specific structure as a catalyst component for olefin polymerization or polymerization catalyst for the production of metallocene polyethylene with a sufficient number and appropriate length of long-chain branches. Patent Document 2 discloses that there is a concern that introducing long-chain branching to improve moldability may reduce mechanical properties. Instead of introducing long-chain branching, a method is disclosed in which the molecular weight distribution is controlled by two-step polymerization using a binary catalyst combining a specific cross-linked cyclopentadienyl-fluorenyl complex and a phenoxyimine complex, thereby improving the extensional flow characteristics and moldability.

[0004] Patent Document 3 discloses that a binary catalyst combining a specific crosslinked cyclopentadienyl-fluorenyl complex and a non-crosslinked biscyclopentadienyl complex improves moldability, mechanical properties, and product appearance. Patent Document 4 discloses a method for producing a polymer having a specific amount of long-chain branching using a binary catalyst combining a specific crosslinked biscyclopentadienyl complex and a crosslinked cyclopentadienyl-fluorenyl complex, or a binary catalyst combining a specific crosslinked biscyclopentadienyl complex and a crosslinked indenyl-fluorenyl complex. Patent Document 5 discloses a method for producing polymers with a broad molecular weight distribution by performing multi-step polymerization in the presence of a binary catalyst combining a specific non-crosslinked biscyclopentadienyl complex and a specific crosslinked bisindenyl complex. Patent Document 6 discloses that by using a catalyst that combines a specific non-crosslinked biscyclopentadienyl complex, a specific crosslinked metallocene complex or non-crosslinked biscyclopentadienyl complex, and a specific solid oxide, polyethylene polymers with improved film moldability, mechanical properties, and transparency can be obtained. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2012-214780 [Patent Document 2] Japanese Patent Publication No. 2017-25160 [Patent Document 3] Special Publication No. 2009-527636 [Patent Document 4] Japanese Patent Publication No. 2006-321991 [Patent Document 5] Special Publication No. 2002-504958 [Patent Document 6] Japanese Patent Publication No. 2011-140658 [Overview of the project] [Problems that the invention aims to solve]

[0006] As described above, numerous metallocene catalyst technologies have been developed, but polymers obtained using conventional metallocene catalysts still suffer from an insufficient balance of moldability, strength, and durability, and there is a demand for technologies that can improve this.

[0007] The present invention aims to provide a catalyst for olefin polymerization that can produce ethylene-based polymers with an excellent balance of moldability, strength, and durability. Furthermore, the present invention aims to provide a method for producing an ethylene-based polymer with an excellent balance of moldability, strength, and durability using the above-described catalyst for olefin polymerization. [Means for solving the problem]

[0008] The olefin polymerization catalyst of the present invention is characterized by comprising the following components (A), (B), (C), and (D). Component (A): Metallocene compound represented by the following general formula (1) Component (B): Metallocene compound represented by the following general formula (2) Component (C): A compound that makes component (A) and component (B) cationic compounds. Component (D): Particulate carrier

[0009] [ka]

[0010] [In formula (1), M 1 This represents a titanium atom, a zirconium atom, or a hafnium atom. X 1 and X 2 Each of these 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, a hydrocarbon group having 3 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms. R 1 , R2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent 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 alkoxyalkyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group whose alkyl group has 1 to 3 carbon atoms, a substituted silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, or an optionally substituted 5-membered or 6-membered heterocyclic group.]

[0011]

Chemical Formula

[0012] [In formula (2), M 2 represents a titanium atom, a zirconium atom or a hafnium atom. X 3 and X 4 each independently represent 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 substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms. Y represents a carbon atom, a silicon atom or a germanium atom. R 11 and R 21 each independently represent 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 , R22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 and R 29 Each independently represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C6 alkenyl group, a C1-C6 alkyl group substituted with a halogen atom, a C1-C6 alkyl group whose alkyl group is substituted with a C1-C3 trialkylsilyl group, a substituted silyl group substituted with a C1-C6 hydrocarbon group, an aryl group 6-C18, an aryl group substituted with a halogen atom, or a heterocyclic group constituting a 5-membered or 6-membered ring which may have substituents. 12 ~R 19 and R 22 ~R 29 Adjacent groups may bond to each other to form a 6-7 membered ring, and this 6-7 membered ring may contain unsaturated bonds. R 31 and R 32 Each independently represents a hydrogen atom, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C1-C6 alkyl group substituted with a halogen atom, a C1-C6 alkyl group whose alkyl group is substituted with a C1-C3 trialkylsilyl group, a substituted silyl group substituted with a C1-C6 hydrocarbon group, an aryl group 6-C18, an aryl group substituted with a halogen atom, or a heterocyclic group constituting a 5-membered or 6-membered ring which may have substituents. 31 and R 32 Y may form a 4-7 membered ring, and R 31 and R 32 If at least one of them has a ring structure, R 31 , R 32 The 4-7 member ring composed of and Y is R 31 and R 32 It may form a fused ring that shares some of the constituent atoms of the cyclic structure it possesses.

[0013] In the olefin polymerization catalyst of the present invention, an ethylene polymer with an excellent balance of moldability, strength, and durability is easily obtained, and in the general formula (2) of component (B), R 11 and R 21 The base may be represented by the following general formula (3).

[0014] [ka] [In formula (3), Z is an oxygen atom or a sulfur atom, R 33 , R 34 Each of these is independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C8 alkenyl group, a C1-C6 alkyl group substituted with a halogen atom, a C6-C18 aryl group, a C6-C18 aryl group substituted with a halogen atom, a C1-C3 alkyl group in which the alkyl group is substituted with a C1-C3 trialkylsilyl group, or a substituted silyl group substituted with a C1-C6 hydrocarbon group, and R 33 and R 34 These elements may bond to each other to form a 6-7 membered ring, and this 6-7 membered ring may contain unsaturated bonds.

[0015] In the olefin polymerization catalyst of the present invention, an ethylene polymer with an excellent balance of moldability, strength, and durability is easily obtained, and in the general formula (1) of component (A), R 1 and R 6 However, each is independently an alkyl group having 3 to 6 carbon atoms, and R 3 and R 8 However, each is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 2 , R 4 , R 5 , R 7 , R 9 and R 10 It may be a hydrogen atom.

[0016] In the olefin polymerization catalyst of the present invention, an ethylene polymer with an excellent balance of moldability, strength, and durability is easily obtained, and in the general formula (1) of component (A), R 1 and R 6 However, each is independently an alkyl group having 3 to 6 carbon atoms, and R 3 and R 8 However, each is independently a hydrogen atom or a methyl group, R 2 , R 4 , R 5 , R 7 , R 9 and R 10 It may be a hydrogen atom.

[0017] In the olefin polymerization catalyst of the present invention, an ethylene polymer with an excellent balance of moldability, strength, and durability is easily obtained, and in the general formula (1) of component (A), R 1 and R 6 However, each is independently an alkyl group having 3 to 6 carbon atoms, and R 3 and R 8 is a hydrogen atom, and R 2 , R 4 , R 5 , R 7 , R 9 and R 10 It may be a hydrogen atom.

[0018] In the olefin polymerization catalyst of the present invention, component (C) may be methylaluminoxane, from the standpoint of industrial availability and polymer particle properties.

[0019] The present invention provides a method for producing an ethylene-based polymer, characterized by polymerizing ethylene, or ethylene and an α-olefin having 3 to 10 carbon atoms, in the presence of the olefin polymerization catalyst of the present invention described above.

[0020] In the method for producing ethylene-based polymers of the present invention, slurry polymerization may be used from the viewpoint of controlling the properties of polymer particles. [Effects of the Invention]

[0021] According to the present invention, it is possible to provide an olefin polymerization catalyst that can produce ethylene-based polymers with high melt tension, excellent moldability, high strength and durability, and an excellent balance of moldability, strength and durability. Furthermore, by using the olefin polymerization catalyst of the present invention, it is possible to provide a method for producing ethylene-based polymers with an excellent balance of moldability, strength, and durability. [Brief explanation of the drawing]

[0022] [Figure 1] Figure 1 shows the GPC charts of the ethylene polymers obtained in Example 1 and Comparative Example 1. [Figure 2] Figure 2 shows the GPC charts for the ethylene polymers obtained in Reference Example 1, Reference Example 2, and Reference Example 3. [Figure 3] Figure 3 shows the viscoelasticity measurements of the blended products obtained in Reference Example 1 and Reference Example 3. [Modes for carrying out the invention]

[0023] The present invention will be described below. In this invention, "polymerization" refers collectively to the homopolymerization of one type of monomer and the copolymerization of multiple types of monomers. When there is no need to distinguish between the two, the term "polymerization" is used collectively. Furthermore, in this invention, the "~" indicating a numerical range is used to mean that the numerical values ​​written before and after it are included as the lower and upper limits, respectively. Furthermore, in this invention, "i-" refers to iso, "n-" to normal, "s-" to secondary, and "t-" to tertiary isomer structures. For example, when simply referred to as "butyl," it is used to mean the normal structure.

[0024] I. Catalysts for Olefin Polymerization The olefin polymerization catalyst of the present invention is characterized by comprising a metallocene compound represented by general formula (1) described later (component (A)), a metallocene compound represented by general formula (2) described later (component (B)), a compound that converts component (A) and component (B) into cationic compounds (component (C)), and a fine particle carrier (component (D)).

[0025] Polymers obtained using conventional metallocene catalysts still suffer from an insufficient balance of moldability, strength, and durability. For example, in the method for producing polymers with a broad molecular weight distribution using a binary catalyst described in Patent Document 5, copolymers containing an excess number of high molecular weight long-chain branches are easily obtained, resulting in high viscosity polymers. As shown in Comparative Example 1, when the viscosity is adjusted to the desired level suitable for moldability, a large amount of low molecular weight components are present, leading to problems with poor mechanical strength and durability. In contrast, using the olefin polymerization catalyst of the present invention allows for the production of polymers with excellent moldability, strength, and durability, as they maintain high impact strength while also exhibiting high melt tension and durability. This is thought to be due to the structures of components (A) and (B), which are metallocene complexes contained in the olefin polymerization catalyst of the present invention. In polymerization carried out in the presence of the olefin polymerization catalyst of the present invention, a polymer containing relatively low molecular weight macromonomers is mainly produced by component (A), and at the same time, a relatively high molecular weight copolymer is produced by copolymerization of olefin monomers and macromonomers by component (B). Simultaneously, relatively high molecular weight macromonomers are also produced from component (B), which promotes copolymerization, albeit at a low frequency, resulting in copolymerization with these high molecular weight macromonomers. That is, copolymerization with relatively low molecular weight macromonomers derived from component (A) and copolymerization with relatively high molecular weight macromonomers derived from component (B) occur. Of these, copolymers obtained from copolymerization with high molecular weight macromonomers are undesirable because an excessive number of high molecular weight long-chain branches leads to an excessive increase in viscosity. In component (B) used in the present invention, the heteroatom in the furyl or thienyl group contained in the 2-position substituent of the indene skeleton interacts with the central metal, which is the polymerization-active species. This moderately hinders the coordination of macromonomers to the central metal, thus moderately reducing the copolymerization frequency with relatively high molecular weight macromonomers. On the other hand, in conventional complexes that do not have the specific substituent of the present invention at the 2-position substituent of the indene skeleton, high molecular weight macromonomers also easily coordinate to the central metal, and copolymerization with high molecular weight macromonomers proceeds moderately, resulting in a polymer containing many high molecular weight long-chain branches. Thus, polymerization carried out in the presence of the olefin polymerization catalyst of the present invention can produce a high molecular weight polymer with a moderately broad molecular weight distribution while suppressing the generation of an excess number of high molecular weight long-chain branches, which leads to high viscosity of the polymer. Therefore, the resulting polymer is expected to have a relatively small amount of low molecular weight components in the polymer relative to the HLMFR, maintaining high impact strength, high melt tension, and high durability.

[0026] Hereinafter, each component contained in the olefin polymerization catalyst of the present invention and the method for producing the olefin polymerization catalyst of the present invention will be described.

[0027] 1. Component (A) Component (A) used in the present invention is a metallocene compound represented by the following general formula (1).

[0028]

Chemical Formula

[0029] [In formula (1), M 1 represents a titanium atom, a zirconium atom or a hafnium atom. X 1 and X 2 each independently represent 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 substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent 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 alkoxyalkyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms substituted with a trialkylsilyl group whose alkyl groups each have 1 to 3 carbon atoms, a substituted silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms substituted with a halogen atom, or a heterocyclic group that constitutes a 5- or 6-membered ring which may have a substituent.]]

[0030] M 1The atom is a titanium atom (Ti), a zirconium atom (Zr), or a hafnium atom (Hf), and among these, a zirconium atom is preferred from the viewpoint of molecular weight and activity.

[0031] X 1 and X 2 Each of these is independently a substituted amino group, which 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. Specific examples of halogen atoms include, for instance, chlorine, bromine, iodine, and fluorine atoms. Specific examples of hydrocarbon groups having 1 to 20 carbon atoms include alkyl or cycloalkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, octyl, cyclopropyl, cyclopentyl, and cyclohexyl groups; alkenyl groups such as vinyl, propenyl, butenyl, hexenyl, and cyclohexenyl groups; and alicyclic substituents such as cyclopentylmethyl and 2-cyclohexylethyl groups. Examples include alkyl groups; monocyclic or fused ring aryl groups which may be substituted with saturated or unsaturated hydrocarbon groups such as phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-t-butylphenyl group, 3,5-di-t-butylphenyl group, 4-vinylphenyl group, 3-allylphenyl group, 4-(3-butenyl)phenyl group, naphthyl group, etc.; alkyl groups having aromatic substituents such as benzyl group, 2-phenylethyl group, etc. Specific examples of alkoxy groups having 1 to 20 carbon atoms include, for example, the methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, and phenoxy group. A hydrocarbon group having 3 to 20 carbon atoms containing an oxygen atom or a nitrogen atom may be a hydrocarbon group having 3 to 20 carbon atoms containing at least one oxygen atom or a nitrogen atom. Specific examples include the following: Alkoxyalkyl groups such as ethoxymethyl, n-propoxymethyl, i-propoxymethyl, n-butoxymethyl, i-butoxymethyl, t-butoxymethyl, methoxyethyl, ethoxyethyl, 4-methoxybutyl, 3-ethoxybutyl, and 6-methoxyhexyl; alkoxyaryl groups such as 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, and 2,4-dimethoxyphenyl; acetyl, 1-oxopropyl, 1-oxo-n-butyl, 2-methyl-1-oxopropyl, 2,2-dimethyl-1-oxopropyl, phenylacetyl, diphenylacetyl, and benzoyl groups. Examples of amino-substituted alkyl groups include cyclic ether groups such as elementary groups, 2-furyl groups, 2-tetrahydrofuryl groups, and 2-methylfuryl groups; and amino-substituted aryl groups such as dimethylaminomethyl group, diethylaminomethyl group, di-i-propylaminomethyl group, bis(dimethylamino)methyl group, bis(di-i-propylamino)methyl group, (dimethylamino)(phenyl)methyl group, aminoethyl group, dimethylaminoethyl group, diethylaminoethyl group, 1-(methylimino)ethyl group, 1-(phenylimino)ethyl group, 1-[(phenylmethyl)imino]ethyl group, dimethylaminohexyl group, 4-aminophenyl group, and 4-dimethylaminophenyl group. A substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms may be a substituted amino group substituted with at least one hydrocarbon group having 1 to 20 carbon atoms. Specific examples include dimethylamino group, diethylamino group, di-n-propylamino group, di-i-butylamino group, di-t-butylamino group, and diphenylamino group.

[0032] R 1 , R 2 , R 3 , R 4 , R 5 , R6 , R 7 , R 8 , R 9 and R 10 Each of these is independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C6 alkoxyalkyl group, a C2-C6 alkenyl group, a C1-C6 alkyl group substituted with a halogen atom, a C1-C6 alkyl group in which the alkyl group is substituted with a C1-C3 trialkylsilyl group, a substituted silyl group substituted with a C1-C6 hydrocarbon group, a C6-C18 aryl group, a C6-C18 aryl group substituted with a halogen atom, or a heterocyclic group constituting a 5-membered or 6-membered ring which may have substituents. A specific example of a halogen atom is, for example, the above X. 1 and X 2 The same specific examples of halogen atoms described earlier can be given. Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, cyclopropyl group, cyclopentyl group, and cyclohexyl group. Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, t-butoxy, and phenoxy groups. Examples of alkoxyalkyl groups having 2 to 6 carbon atoms include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, t-butoxymethyl group, methoxyethyl group, ethoxyethyl group, 4-methoxybutyl group, and 3-ethoxybutyl group. Examples of alkenyl groups having 2 to 6 carbon atoms include vinyl, propenyl, butenyl, hexenyl, and cyclohexenyl groups. The C1-C6 alkyl group substituted with a halogen atom may be any C1-C6 alkyl group substituted with at least one halogen atom, and examples include bromomethyl group, chloromethyl group, trifluoromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2,2-trifluoroethyl group, 2-bromopropyl group, 3-bromopropyl group, 3,3,3-trifluoropropyl group, 4-chlorobutyl group, 3-fluorobutyl group, and 4,4,4-trifluorobutyl group. Examples of alkyl groups having 1 to 6 carbon atoms, in which the alkyl group is substituted with a trialkylsilyl group having 1 to 3 carbon atoms, include trimethylsilylmethyl group, trimethylsilylethyl group, and 2-trimethylsilylpropyl group. A substituted silyl group substituted with a hydrocarbon group having 1 to 6 carbon atoms may be a substituted silyl group substituted with at least one hydrocarbon group having 1 to 6 carbon atoms, for example, a trimethylsilyl group or a t-butyldimethylsilyl group. Examples of aryl groups having 6 to 18 carbon atoms include phenyl, naphthyl, and biphenyl groups. The C6-C18 aryl group substituted with a halogen atom may be any C6-C18 aryl group substituted with at least one halogen atom, such as 2-chlorophenyl, 4-chlorophenyl, 3,5-dichlorophenyl, and 2,3,4,5,6-pentafluorophenyl. Examples of heterocyclic groups constituting a five-membered or six-membered ring that may have substituents include heterocyclic groups constituting a five-membered or six-membered ring that may have at least one substituent, such as nitrogen-containing heterocyclic groups like pyrrole groups and pyridine groups, oxygen-containing heterocyclic groups like furan groups and pyran groups, sulfur-containing heterocyclic groups like thiophene groups, and groups in which these heterocyclic groups are substituted with substituents such as alkyl or alkoxy groups having 1 to 30 carbon atoms.

[0033] Among them, R 1 and R6 However, each is independently an alkyl group having 3 to 6 carbon atoms, and R 3 and R 8 However, each is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 2 , R 4 , R 5 , R 7 , R 9 and R 10 R may be a hydrogen atom, 1 and R 6 However, each is independently an alkyl group having 3 to 6 carbon atoms, and R 3 and R 8 However, each is independently a hydrogen atom or a methyl group, R 2 , R 4 , R 5 , R 7 , R 9 and R 10 R may be a hydrogen atom, 1 and R 6 However, each is independently an alkyl group having 3 to 6 carbon atoms, and R 3 and R 8 However, it is a hydrogen atom, R 2 , R 4 , R 5 , R 7 , R 9 and R 10 It may be a hydrogen atom.

[0034] Specific examples of metallocene compounds represented by formula (1) include, for example, Biscyclopentadienylzirconium dichloride, Bis(methylcyclopentadienyl)zirconium dichloride, Bis(n-propylcyclopentadienyl)zirconium dichloride, Bis(i-propylcyclopentadienyl)zirconium dichloride, Bis(n-butylcyclopentadienyl)zirconium dichloride, Bis(s-butylcyclopentadienyl)zirconium dichloride, Bis(t-butylcyclopentadienyl)zirconium dichloride, Bis(n-hexylcyclopentadienyl)zirconium dichloride, Bis(cyclohexylcyclopentadienyl)zirconium dichloride, Bis(1,3-dimethylcyclopentadienyl)zirconium dichloride, Bis(1,3-di-n-propylcyclopentadienyl)zirconium dichloride, Bis(1,3-di-i-propylcyclopentadienyl)zirconium dichloride, Bis(1,3-di-n-hexylcyclopentadienyl)zirconium dichloride, Bis(1,2-di-n-propylcyclopentadienyl)zirconium dichloride, Bis(1,2-di-i-propylcyclopentadienyl)zirconium dichloride, Bis(1,2,4-trimethylcyclopentadienyl)zirconium dichloride, Bis(pentamethylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-ethylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-n-propylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-i-propylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-i-butylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-s-butylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-t-butylcyclopentadienyl)zirconium dichloride, Bis(1-ethyl-3-n-propylcyclopentadienyl)zirconium dichloride, Bis(1-ethyl-3-i-propylcyclopentadienyl)zirconium dichloride, (Methylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride, (Methylcyclopentadienyl)(i-butylcyclopentadienyl)zirconium dichloride, (Methylcyclopentadienyl)(s-butylcyclopentadienyl)zirconium dichloride, (Methylcyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride, (n-Propylcyclopentadienyl)(n-Butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(i-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(s-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride, (i-propylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride, (i-Propylcyclopentadienyl)(i-Butylcyclopentadienyl)zirconium dichloride, (i-Propylcyclopentadienyl)(s-Butylcyclopentadienyl)zirconium dichloride, (i-propylcyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride, Bis(4-methoxybutylcyclopentadienyl)zirconium dichloride, Bis(butoxycyclopentadienyl)zirconium dichloride, Bis(butenylcyclopentadienyl)zirconium dichloride, Bis(trifluoromethylcyclopentadienyl)zirconium dichloride, Bis(trimethylsilylcyclopentadienyl)zirconium dichloride, Bis(phenylcyclopentadienyl)zirconium dichloride, and Examples include bis(n-butylcyclopentadienyl)hafnium dichloride. Among these, it is preferable to use at least one selected from the group consisting of bis(n-propylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(1-methyl-3-n-propylcyclopentadienyl)zirconium dichloride, and bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, as it is easier to obtain an ethylene-based polymer with an excellent balance of moldability, strength, and durability. The metallocene compound represented by formula (1) can be appropriately manufactured by conventionally known methods, and commercially available compounds can also be used.

[0035] 2. Ingredient (B) The component (B) used in the present invention is a metallocene compound represented by the following general formula (2).

[0036] [ka]

[0037] [In formula (2), M 2 This represents a titanium atom, a zirconium atom, or a hafnium atom. X 3 and X 4 Each of these 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, a hydrocarbon group having 3 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, or a substituted amino group substituted with a hydrocarbon group having 1 to 20 carbon atoms. Y represents a carbon atom, a silicon atom, or a germanium atom. R 11 and R 21 Each of these independently represents 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 , R19 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 and R 29 Each independently represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C6 alkenyl group, a C1-C6 alkyl group substituted with a halogen atom, a C1-C6 alkyl group whose alkyl group is substituted with a C1-C3 trialkylsilyl group, a substituted silyl group substituted with a C1-C6 hydrocarbon group, an aryl group 6-C18, an aryl group substituted with a halogen atom, or a heterocyclic group constituting a 5-membered or 6-membered ring which may have substituents. 12 ~R 19 and R 22 ~R 29 Adjacent groups may bond to each other to form a 6-7 membered ring, and this 6-7 membered ring may contain unsaturated bonds. R 31 and R 32 Each independently represents a hydrogen atom, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C1-C6 alkyl group substituted with a halogen atom, a C1-C6 alkyl group whose alkyl group is substituted with a C1-C3 trialkylsilyl group, a substituted silyl group substituted with a C1-C6 hydrocarbon group, an aryl group 6-C18, an aryl group substituted with a halogen atom, or a heterocyclic group constituting a 5-membered or 6-membered ring which may have substituents. 31 and R 32 Y may form a 4-7 membered ring, and R 31 and R 32 If at least one of them has a ring structure, R 31 , R 32 The 4-7 member ring composed of and Y is R 31 and R 32 It may form a fused ring that shares some of the constituent atoms of the cyclic structure it possesses.

[0038] M 2The catalyst is a titanium atom (Ti), a zirconium atom (Zr), or a hafnium atom (Hf), and among these, a zirconium atom is preferred from the viewpoint of high catalyst activation.

[0039] X 3 and X 4 Each of these is independently a substituted amino group, which 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. X 3 and X 4 A concrete example of this is X in equation (1) above. 1 and X 2 A concrete example explaining X 3 and X 4 This can also be mentioned.

[0040] Y is a carbon atom, a silicon atom, or a germanium atom, and among these, a silicon atom is preferred from the viewpoint of complex synthesis.

[0041] R 11 and R 21 Each of these is independently a substituted furyl group or a substituted thienyl group, and may be at least one substituted furyl group or a substituted thienyl group. Examples of substituents that the furyl group or thienyl group may have include halogen atoms, C1-C6 alkyl groups, C1-C6 alkoxy groups, C1-C6 alkyl groups substituted with halogen atoms, C1-C6 alkyl groups in which the alkyl group is substituted with a C1-C3 trialkylsilyl group, C6-C18 aryl groups which may be substituted with a C1-C6 alkyl group, C6-C18 aryl groups which are substituted with halogen atoms, and substituted silyl groups which are substituted with a C1-C6 hydrocarbon group. Specific examples of halogen atoms, C1-C6 alkyl groups, C1-C6 alkoxy groups, C1-C6 alkyl groups substituted with halogen atoms, C1-C6 alkyl groups in which the alkyl group is substituted with a C1-C3 trialkylsilyl group, C6-C18 aryl groups which are substituted with halogen atoms, and substituted silyl groups which are substituted with a C1-C6 hydrocarbon group are the same as those mentioned above. A C6-C18 aryl group that may be substituted with a C1-C6 hydrocarbon group may be a C6-C18 aryl group that may be substituted with at least one C1-C6 hydrocarbon group. Specific examples include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,4,6-trimethylphenyl group, 2,3,4-trimethylphenyl group, and 2,3,4-trimethylphenyl group. Examples include methylphenyl group, 2,4,5-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2-i-propylphenyl group, 3-i-propylphenyl group and 4-i-propylphenyl group, 2-t-butylphenyl group, 3-t-butylphenyl group, 4-t-butylphenyl group, 2,4-di-t-butylphenyl group, 2.5-di-t-butylphenyl group, 2,6-di-t-butylphenyl group, 3,5-di-t-butylphenyl group, biphenylyl group, 1-naphthyl group, 2-naphthyl group, acenaphthyl group, phenanthryl group, and anthryl group. Furthermore, the substituents that the furyl group or thienyl group may have may be bonded together by adjacent substituents to form a 6-7 membered ring, and the 6-7 membered ring may contain unsaturated bonds.

[0042] Because it is easy to obtain ethylene-based polymers with an excellent balance of moldability, strength, and durability, R 11 and R 21 Preferably, the group is represented by the following formula (3).

[0043] [ka]

[0044] [In formula (3), Z is an oxygen atom or a sulfur atom, R 33 , R 34 Each of these is independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C8 alkenyl group, a C1-C6 alkyl group substituted with a halogen atom, a C6-C18 aryl group, a C6-C18 aryl group substituted with a halogen atom, a C1-C3 alkyl group in which the alkyl group is substituted with a C1-C3 trialkylsilyl group, or a substituted silyl group substituted with a C1-C6 hydrocarbon group, and R 33 and R 34 These elements may bond to each other to form a 6-7 membered ring, and this 6-7 membered ring may contain unsaturated bonds.

[0045] Z is either an oxygen atom or a sulfur atom, and it is preferably an oxygen atom because it is easier to obtain an ethylene-based polymer with an excellent balance of moldability, strength, and durability.

[0046] R 33 , R 34Each of these is independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C8 alkenyl group, a C1-C6 alkyl group substituted with a halogen atom, a C6-C18 aryl group, a C6-C18 aryl group substituted with a halogen atom, a C1-C3 alkyl group in which the alkyl group is substituted with a C1-C3 trialkylsilyl group, or a substituted silyl group substituted with a C1-C6 hydrocarbon group, and R 33 and R 34 These elements may bond to each other to form a 6-7 membered ring, and this 6-7 membered ring may contain unsaturated bonds. A specific example of a halogen atom is, for example, the above X. 1 and X 2 We can give the same specific examples of halogen atoms that were explained earlier. Specific examples of alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, alkyl groups having 1 to 6 carbon atoms substituted with halogen atoms, aryl groups having 6 to 18 carbon atoms, aryl groups having 6 to 18 carbon atoms substituted with halogen atoms, and substituted silyl groups having 1 to 6 carbon atoms include, for example, the above R 1 ~R 10 The same specific examples described earlier can be given. Specific examples of alkenyl groups having 2 to 8 carbon atoms include, for example, the above R 1 ~R 10 Examples of alkenyl groups with 2 to 6 carbon atoms, as explained above, include the heptenyl group and the octenyl group. Specific examples of C1-C3 alkyl groups substituted with C1-C3 trialkylsilyl groups include, for example, trimethylsilylethyl group, triethylsilylethyl group, 2-trimethylsilylpropyl group, and 2-triethylsilylpropyl group.

[0047] Because it is easy to obtain ethylene-based polymers with an excellent balance of moldability, strength, and durability, R 33The substituted silyl group is preferably a halogen atom, a C1-C6 alkyl group, a C6-C18 aryl group, or a C1-C6 hydrocarbon group, and more preferably a substituted silyl group is substituted with a C1-C6 alkyl group, a C6-C18 aryl group, or a C1-C6 hydrocarbon group. 34 Preferably, is a hydrogen atom, a halogen atom, a C1-C6 alkyl group, or a C6-C18 aryl group, more preferably a hydrogen atom or a C1-C6 alkyl group.

[0048] Specific examples of furyl groups that may be substituted include 2-furyl group, 2-(5-methylfuryl) group, 2-(5-ethylfuryl) group, 2-(5-n-propylfuryl) group, 2-(5-i-propylfuryl) group, 2-(5-t-butylfuryl) group, 2-(5-trimethylsilylfuryl) group, 2-(5-triethylsilylfuryl) group, 2-(5-phenylfuryl) group, 2-(5-tolylfuryl) group, 2-(5-fluorophenylfuryl) group, 2-(5-chlorophenylfuryl) group, 2-(4,5-dimethylfuryl) group, and 2-(3,5-dimethyl Examples include the furyl group, 2-benzofuryl group, 3-furyl group, 3-(5-methylfuryl) group, 3-(5-ethylfuryl) group, 3-(5-n-propylfuryl) group, 3-(5-i-propylfuryl) group, 3-(5-t-butylfuryl) group, 3-(5-trimethylsilylfuryl) group, 3-(5-triethylsilylfuryl) group, 3-(5-phenylfuryl) group, 3-(5-tolylfuryl) group, 3-(5-fluorophenylfuryl) group, 3-(5-chlorophenylfuryl) group, 3-(4,5-dimethylfuryl) group, and 3-benzofuryl group. Specific examples of substituted thienyl groups include 2-thienyl group, 2-(5-methylthienyl) group, 2-(5-ethylthienyl) group, 2-(5-n-propylthienyl) group, 2-(5-i-propylthienyl) group, 2-(5-t-butylthienyl) group, 2-(5-trimethylsilylthienyl) group, 2-(5-triethylsilylthienyl) group, 2-(5-phenylthienyl) group, 2-(5-tolylthienyl) group, 2-(5-fluorophenylthienyl) group, 2-(5-chlorophenylthienyl) group, 2-(4,5-dimethylthienyl) group, and 2-(3,5-dimethylthienyl) group. Examples of these groups include the 3-(5-(5-) group, 2-benzothienyl group, 3-thienyl group, 3-(5-methylthienyl) group, 3-(5-ethylthienyl) group, 3-(5-n-propylthienyl) group, 3-(5-i-propylthienyl) group, 3-(5-t-butylthienyl) group, 3-(5-trimethylsilylthienyl) group, 3-(5-triethylsilylthienyl) group, 3-(5-phenylthienyl) group, 3-(5-tolylthienyl) group, 3-(5-fluorophenylthienyl) group, 3-(5-chlorophenylthienyl) group, 3-(4,5-dimethylthienyl) group, 3-benzothienyl group, and the like.

[0049] 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 29Each independently represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, a C2-C6 alkenyl group, a C1-C6 alkyl group substituted with a halogen atom, a C1-C6 alkyl group whose alkyl group is substituted with a C1-C3 trialkylsilyl group, a substituted silyl group substituted with a C1-C6 hydrocarbon group, an aryl group 6-C18, an aryl group substituted with a halogen atom, or a heterocyclic group constituting a 5-membered or 6-membered ring which may have substituents. 12 ~R 19 and R 22 ~R 29 Adjacent groups may bond to each other to form a 6-7 membered ring, and this 6-7 membered ring may contain unsaturated bonds. A specific example of a halogen atom is, for example, the above X. 1 and X 2 We can give the same specific examples of halogen atoms that were explained earlier. Specific examples of heterocyclic groups constituting a 5-membered or 6-membered ring, which may have substituents, include, for example, the above R 1 ~R 10 The same specific examples described earlier can be given.

[0050] Specific examples of metallocene compounds represented by the above formula (2) include, for example, [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-(5-methyl-2-furyl)-4-(4-chlorophenyl)-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trifluoromethylphenyl)-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trimethylsilylphenyl)-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(1-naphthyl)-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(2-naphthyl)-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(2-phenanthryl)-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(9-phenanthuryl)-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(1-naphthyl)-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-naphthyl)-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-phenanthuryl)-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(9-phenanthuryl)-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, Examples include [1,1'-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(9-phenanthuryl)-indenyl}]zirconium dichloride.

[0051] Among these, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-phenyl-indenyl}]zirconium dichloride, and [1,1'-dimethylsilylenebis{2-(5-trimethylsilyl-2-furyl)-4-phenyl-indenyl}]zirconium dichloride are selected because they easily yield ethylene-based polymers with an excellent balance of moldability, strength, and durability. It is preferable to use at least one selected from the group consisting of [1,1'-dimethylsilylenebis{2-(5-phenyl-2-furyl)-4-phenyl-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl}]zirconium dichloride, and [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)-indenyl}]zirconium dichloride.

[0052] When synthesizing the metallocene compound represented by formula (2), for example, one can refer to Synthesis Example 1 in Japanese Patent Publication No. 2012-149160.

[0053] 3.Component (C) Component (C) used in the present invention is a compound that converts components (A) and (B) described above into cationic compounds, and is therefore a co-catalyst. Components (A) and (B) contained in the olefin polymerization catalyst of the present invention may be compounds that have reacted with component (C) to become cationic compounds. For component (C), for example, organoaluminum oxy compounds, borane compounds, borate compounds, and layered silicates described later can be used. Of these, organoaluminum oxy compounds are preferred because they are easy to immobilize onto a fine particle carrier.

[0054] (1) Organoaluminum oxy compounds Organoaluminum oxy compounds are compounds that have Al-O-Al bonds in their molecules, and the number of Al-O-Al bonds is usually in the range of 1 to 100, preferably 1 to 50. Typically, organoaluminum oxy compounds containing a chain structure of -(O-Al)- units, such as those represented by formula (4) or formula (5) below, are used.

[0055] [ka]

[0056] [ka]

[0057] [In each of the above formulas, R 41 Each is independently a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 18 carbon atoms, more preferably an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, and R 41 At least a portion of it is a hydrocarbon group. p represents an integer between 0 and 40, preferably between 2 and 30.

[0058] Such organoaluminum oxy compounds are usually obtained by reacting an organoaluminum compound with water. The reaction between organoaluminum compounds and water is usually carried out in an inert hydrocarbon (solvent). Suitable inert hydrocarbons include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene, as well as alicyclic hydrocarbons and aromatic hydrocarbons. However, the use of aliphatic or aromatic hydrocarbons is preferred.

[0059] As the raw material organoaluminum compound, a compound represented by the following formula (6) can be used, but trialkylaluminum is preferred. R 41 t AlX 6 3-t Formula (6) [In formula (6), R 41 This is the same as equations (4) and (5) above, and X 6 [where 't' represents a hydrogen atom or a halogen atom, and 't' represents an integer between 1 and 3.]

[0060] The alkyl group of trialkylaluminum can be any of the following: methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, etc., but a methyl group is particularly preferred. Two or more of the above organoaluminum compounds can also be used in combination.

[0061] The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is preferably 0.25 / 1 to 1.2 / 1, particularly 0.5 / 1 to 1 / 1. The reaction temperature is usually in the range of -70°C to 100°C, preferably -20°C to 20°C. The reaction time is usually selected from 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As the water required for the reaction, not only plain water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate, etc., and components that can generate water in the reaction system can be used.

[0062] Organoaluminum oxy compounds using trimethylaluminum as the raw material are called methylaluminoxane (MAO). Methylaluminoxane (MAO) is particularly preferred as component (C) due to its industrial availability and ease of controlling polymer particle properties. MAO can also be used as component (C) in a form containing unreacted trimethylaluminum. This unreacted trimethylaluminum may be present in an amount of 1 mol% to 30 mol% relative to the total aluminum atoms of trimethylaluminum and methylaluminoxane. Within this range, MAO is less likely to precipitate in the solution, reducing the risk during handling and making it easier to handle. Preferably, an MAO solution containing 10 mol% to 15 mol% trimethylaluminum is preferred. Furthermore, an MAO concentration within this range reduces the risk during handling, provides good storage stability, and is suitable from a handling standpoint. Preferably, an MAO concentration of 10% to 20% by mass is used. In addition, since MAO solutions tend to precipitate at room temperature, low-temperature storage below -10°C is preferred. Of course, two or more of the above-mentioned organoaluminum oxy compounds can be used in combination as the organoaluminum oxy compound, and a solution or dispersion of the organoaluminum oxy compound in the aforementioned inert hydrocarbon solvent may also be used.

[0063] (2) Borane compounds Examples of borane compounds include the following: 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.

[0064] 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. Among these, the following compounds are even more preferred: tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, and tris(perfluorobiphenyl)borane.

[0065] (3) Borate compounds One example of a borate compound is the compound represented by the following formula (7). [L 1 -H] + [BR 42 R 43 X 7 X 7’ ] - Formula (7)

[0066] In formula (7), L 1 H is a neutral Lewis base, and H is a hydrogen atom, [L1 -H] is a Brønsted acid such as ammonium, anilinium, or phosphonium. Examples of ammonium compounds include trialkyl-substituted ammonium compounds such as trimethylammonium, triethylammonium, tri(n-propyl)ammonium, and tri(n-butyl)ammonium, as well as dialkylammonium compounds such as di(n-propyl)ammonium and dicyclohexylammonium. Examples of anilinium include N,N-dimethylanilinium, N,N-diethylanilinium, and N,N-2,4,6-pentamethylanilinium, which are all N,N-dialkylanilinium species. Furthermore, examples of phosphoniums include triarylphosphoniums and trialkylphosphoniums such as triphenylphosphonium, tri(n-butyl)phosphonium, tri(methylphenyl)phosphonium, and tri(dimethylphenyl)phosphonium.

[0067] Also, in equation (7), R 42 and R 43 Each of these is an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, which may have substituents and may be linked to each other by a crosslinking group. Preferred substituents are alkyl groups such as methyl, ethyl, n-propyl, and i-propyl groups, and halogens such as fluorine, chlorine, bromine, and iodine. Furthermore, X 7 and X 7’ These are, independently, a hydride group, a halide group, a hydrocarbon group having 1 to 20 carbon atoms, and a hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted by halogen atoms.

[0068] Specific examples of compounds represented by the above general formula (7) include, for example, 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 tetraphenyl borate.

[0069] 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.

[0070] A second example of a borate compound is the compound represented by the following formula (8). [L 2 ] + [BR 42 R 43 X 7’ X 7’ ] - Formula (8)

[0071] In formula (8), L 2 Examples include methyl cation, ethyl cation, n-propyl cation, i-propyl cation, n-butyl cation, i-butyl cation, t-butyl cation, n-pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium cation, proton, etc. Also, R 42 , R 43 , X 7 and X 7’ This is the same as the definition in equation (7) above.

[0072] Specific examples of compounds represented by formula (8) above include the following: trityltetraphenyl borate, trityltetra(o-tolyl)borate, trityltetra(p-tolyl)borate, trityltetra(m-tolyl)borate, trityltetra(o-fluorophenyl)borate, trityltetra(p-fluorophenyl)borate, trityltetra(m-fluorophenyl)borate, trityltetra(3,5-difluorophenyl)borate, trityltetra(pentafluorophenyl)borate, trityltetra(2,6-ditrifluoromethylphenyl)borate, trityltetra(3,5-ditrifluoromethylphenyl)borate, trityltetra(perfluoronaphthyl)borate, tropiniumtetraphenyl borate, tropiniumtetra(o-tolyl)borate, tropiniumtetra(p-tolyl)borate, tropiniumtetra(m- Tropium(Tryl)borate, Tropium(o-fluorophenyl)borate, Tropium(p-fluorophenyl)borate, Tropium(m-fluorophenyl)borate, Tropium(3,5-difluorophenyl)borate, Tropium(pentafluorophenyl)borate, Tropium(2,6-ditrifluoromethylphenyl)borate, Tropium(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. In this specification, Et represents ethyl and Ph represents phenyl.

[0073] Among these, the following compounds are preferred: trityltetra(pentafluorophenyl)borate, trityltetra(2,6-ditrifluoromethylphenyl)borate, trityltetra(3,5-ditrifluoromethylphenyl)borate, trityltetra(perfluoronaphthyl)borate, tropiniumtetra(pentafluorophenyl)borate, tropiniumtetra(2,6-ditrifluoromethylphenyl)borate, tropiniumtetra(3,5-ditrifluoromethylphenyl)borate, tropiniumtetra(perfluoronaphthyl)borate, NaB(C6F5)4, NaB(2,6-(CF3)2-Ph)4, NaB(3,5-(CF3)2-Ph)4, NaB(C 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.

[0074] Among these, the following compounds are even more preferred: trityltetra(pentafluorophenyl)borate, trityltetra(2,6-ditrifluoromethylphenyl)borate, tropiniumtetra(pentafluorophenyl)borate, tropiniumtetra(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.

[0075] Furthermore, a mixture of the aforementioned organoaluminum oxy compound and the above-mentioned borane compound or borate compound may be used as component (C). In addition, two or more of the above-mentioned borane compounds or borate compounds may be used in combination.

[0076] 4.Component (D) Component (D), i.e., the fine particle carrier, may 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 as inorganic supports include, for example, iron, aluminum, and nickel.

[0077] Furthermore, examples of metal oxides include single or complex oxides of elements from groups 1 to 14 of the periodic table. For example, various natural or synthetic single or complex oxides such as SiO2, Al2O3, MgO, CaO, B2O3, TiO2, ZrO2, Fe2O3, Al2O3·MgO, Al2O3·CaO, Al2O3·SiO2, Al2O3·MgO·CaO, Al2O3·MgO·SiO2, Al2O3·CuO, Al2O3·Fe2O3, Al2O3·NiO, and SiO2·MgO can be cited. Here, the above formulas represent only the composition, not the molecular formula, and the structure and component ratio of the complex oxides used in the present invention are not particularly limited. In addition, the metal oxides used in the present invention may absorb small amounts of moisture and may contain small amounts of impurities.

[0078] As metal chlorides, alkali metal and alkaline earth metal chlorides are preferred, and specifically MgCl2 and CaCl2 are particularly preferred. As metal carbonates, alkali metal and alkaline earth metal carbonates are preferred, and specifically, magnesium carbonate, calcium carbonate, and barium carbonate are examples. Examples of carbonaceous materials include carbon black and activated carbon. All of the inorganic supports described above can be suitably used in the present invention, but metal oxides, silica, and alumina are preferred, and silica is even more preferred. As for silica, it is preferable to use small-particle silica with an average particle size of about 10 μm to 150 μm. Here, the average particle size is the value expressed as the median diameter from data expressed on a volume basis using a commonly used laser diffraction measurement method.

[0079] These inorganic supports are usually calcined at 200°C to 800°C, preferably 400°C to 600°C, in air or inert gas such as nitrogen or argon, to adjust the amount of surface hydroxyl groups to 0.8 mmol / g to 1.5 mmol / g before use. While there are no particular restrictions on the properties of these inorganic supports, typically the average particle size is 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 m². 2 / g~1000m 2 / g, preferably 200m 2 / g~700m 2 / g, pore volume is 0.3 m³ 3 / g~2.5cm 3 / g, preferably 0.5m 3 / g~2.0cm 3 / g, apparent specific gravity is 0.20 g / cm³ 3 ~0.50g / cm 3 Preferably 0.25 g / cm³ 3 ~0.45g / cm 3 It is preferable to use an inorganic carrier having the following properties.

[0080] The inorganic supports described above can, of course, be used as is, but they can also be used after being pre-treated by contacting them with organoaluminum compounds such as trimethylaluminum, triethylaluminum, tri-i-butylaluminum, tri-n-hexylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, and di-i-butylaluminum hydride, or with organoaluminum oxy compounds containing Al-O-Al bonds.

[0081] 5. Method for producing catalysts for olefin polymerization The olefin polymerization catalyst of the present invention can be produced by mixing or contacting components (A), (B), (C), and (D). The method for producing the olefin polymerization catalyst of the present invention is not particularly limited, but for example, the following methods can be optionally employed. Method (1): Components (A) and (B) are first brought into contact with component (C), and then into contact with component (D). More specifically, components (A) and (B) are brought into contact with a single component (C), or components (A) and (B) are each brought into contact with a separately separated component (C), and then the resulting contacted product is brought into contact with component (D). When bringing components (A) and (B) into contact with a single component (C), a mixture of components (A) and (B) may be brought into contact with component (C), or components (A) and (B) may be brought into contact with component (C) simultaneously or sequentially. When components (A) and (B) are brought into contact with a separately separated component (C), the contacted material of component (A) and the contacted material of component (B) may be brought into contact with a single component (D), or the contacted material of component (A) and the contacted material of component (B) may be brought into contact with a separately separated component (C), and then the two resulting contacted materials may be mixed. Method (2): Components (A) and (B) are first brought into contact with component (D), and then into contact with component (C). More specifically, components (A) and (B) are brought into contact with a single component (D), or components (A) and (B) are each brought into contact with a separately separated component (D), and then the resulting contacted product is brought into contact with component (C). When bringing components (A) and (B) into contact with a single component (D), a mixture of components (A) and (B) may be brought into contact with component (D), or components (A) and (B) may be brought into contact with component (D) simultaneously or sequentially. When components (A) and (B) are brought into contact with component (D) separately, the contacted material of component (A) and the contacted material of component (B) may be brought into contact with a single component (C), or the contacted material of component (A) and the contacted material of component (B) may be brought into contact with component (C) separately, and then the two resulting contacted materials may be mixed. Method (3): After first bringing components (C) and (D) into contact to obtain a contact material, components (A) and (B) are brought into contact with the contact material. More specifically, after bringing components (C) and (D) into contact to obtain a contact material, components (A) and (B) are brought into contact with a single contact material, or components (A) and (B) are brought into contact with separate contact materials, and the two resulting contact materials are mixed. When bringing components (A) and (B) into contact with a single contact object, a mixture of components (A) and (B) may be brought into contact with the contact object, or components (A) and (B) may be brought into contact with the contact object simultaneously or sequentially.

[0082] Among these contact methods, method (1), in which components (A) and (B) are first brought into contact with component (C), and method (3), in which components (A) and (B) are brought into contact with a product containing components (C) and (D), with method (1) being the most preferred. Furthermore, it is preferable to bring a mixture of components (A) and (B) into contact with component (C), component (D), or a product containing components (C) and (D).

[0083] In any contact method, the components are typically brought into contact with each other under stirring or without stirring, in an inert atmosphere such as nitrogen or argon, generally in the presence of liquid inert hydrocarbons such as aromatic hydrocarbons (usually with 6 to 12 carbon atoms) including benzene, toluene, xylene, and ethylbenzene, and aliphatic or alicyclic hydrocarbons (usually with 5 to 12 carbon atoms) including heptane, hexane, decane, dodecane, and cyclohexane. This contact is preferably carried out at a temperature of -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. Specific examples of contact methods include mixing a mixture of component (A) and component (B), or a solution in which components (A) and (B) are dissolved or dispersed in an inert solvent as described above, with a solution in which component (C) is dissolved or dispersed in an inert solvent, and then mixing the resulting mixture with a slurry of component (D).

[0084] Furthermore, when components (A), (B), (C), and (D) come into contact, both aromatic hydrocarbon solvents in which certain components are soluble or sparingly soluble, and aliphatic or alicyclic hydrocarbon solvents in which certain components are insoluble or sparingly soluble, can be used.

[0085] When the contact reactions between components are carried out in steps, the solvent used in the preceding step may be used directly as the solvent for the subsequent contact reaction without removing it. Alternatively, after the initial contact reaction using a soluble solvent, a liquid inert hydrocarbon in which certain components are insoluble or sparingly soluble (for example, aliphatic hydrocarbons, alicyclic hydrocarbons, or aromatic hydrocarbons such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, and xylene) may be added to recover the desired product as a solid, or after removing part or all of the soluble solvent by means of drying or other means to obtain 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. The present invention does not prevent the contact reactions of each component from being carried out multiple times.

[0086] In the present invention, the proportions of component (A), component (B), component (C), and component (D) used are not particularly limited, but the following ranges are preferred. The molar ratio of component (A) to component (B) (component (A):component (B)) is arbitrarily adjusted to determine the shape of the molecular weight distribution of the resulting polymer, and is typically in the range of 1:500 to 500:1, preferably 1:100 to 100:1, more preferably 1:10 to 10:1, and may be in the range of 1.2:1 to 5:1. When an organoaluminum oxy compound is used as component (C), the molar ratio of aluminum atoms in the organoaluminum oxy compound to the total amount of transition metal (M) contained in components (A) and (B) (Al / M) is usually in the range of 1 to 100,000, preferably 5 to 1,000, and more preferably 50 to 200. Furthermore, when a borane compound or borate compound is used, the molar ratio of boron atoms to the total amount of transition metal (M) contained in components (A) and (B) (B / M) is usually in the range of 0.01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10. Furthermore, when using a mixture of organoaluminum oxy compounds, borane compounds, and borate compounds as component (C), it is desirable to select each compound in the mixture in the same proportion as described above relative to the total amount of transition metal (M) contained in components (A) and (B).

[0087] The amount of component (D) used is such that the total amount of transition metals contained in components (A) and (B) is 0.0001 mmol to 5 mmol per gram of component (D), preferably 0.001 mmol to 0.5 mmol, and more preferably 0.01 mmol to 0.1 mmol.

[0088] An olefin polymerization catalyst can be obtained by bringing components (A), (B), (C), and (D) into contact with each other using any of the contact methods (1) to (3) described above. However, after the contact step, a washing step may be performed to remove unreacted substances and unwanted products, and then the solvent may be removed. In the washing process, methods such as allowing the olefin polymerization catalyst to settle, then removing the unnecessary supernatant, adding a new solvent and stirring to homogenize it, repeating the stirring and homogenization process, or washing using a filter device are employed. The solvent used in the washing process is one that can be used in contact with components (A) to (D). The solvent can also be changed during the washing process. For the solvent removal process, methods such as distillation, in which the solvent is evaporated at a pressure corresponding to the boiling point of the solvent, or vaporization, in which the solvent is vaporized by a stream of dry inert gas, can be used. It is desirable to remove the solvent under normal pressure or reduced pressure, at 0°C to 200°C, preferably 20°C to 150°C, for 1 minute to 50 hours, preferably 10 minutes to 10 hours. The olefin polymerization catalyst obtained after the washing step can be handled or stored in slurry form, and the olefin polymerization catalyst obtained in the solvent removal step can be handled or stored as a powdered solid catalyst.

[0089] Furthermore, the olefin polymerization catalyst of the present invention can also be obtained by the following method. Method (4): Components (A) and (B) are brought into contact with component (D), which is a fine particle carrier, to remove the solvent. This is then converted into a solid catalyst component and brought into contact with component (C), which is a co-catalyst, under polymerization conditions. Method (5): The co-catalyst component (C) and the fine particle carrier component (D) are brought into contact to remove the solvent, and this is converted into a solid catalyst component, which is then brought into contact with the catalytically active components (A) and (B) under polymerization conditions. In the cases of methods (4) and (5) described above, the same conditions as described above can be adopted for the component ratio, contact conditions, and solvent removal conditions.

[0090] Furthermore, layered silicates can be used as a component that serves as both a co-catalyst (C) and a fine particle carrier (D). Layered silicates are silicate compounds that have a crystalline structure in which planes formed by ionic bonds, etc., are stacked parallel to each other with weak bonding forces. Most layered silicates occur naturally mainly as the main component of clay minerals, but these layered silicates are not limited to natural products and may also be artificially synthesized. Among these, smectites such as montmorillonite, sauconite, bidelite, nontronite, saponite, hectorite, stevensite, bentonite, and teniolite, as well as vermiculites and micas, are preferred.

[0091] Generally, natural products are often non-ion-exchangeable (non-swelling), and in such cases, it is preferable to perform a treatment to impart ion-exchangeability (or swelling) to achieve desirable ion-exchangeability (or swelling). Among such treatments, the following chemical treatments are particularly preferred. Here, chemical treatment can be either a surface treatment to remove impurities adhering to the surface or a treatment that affects the crystal structure and chemical composition of the layered silicate. Specifically, these include (a) acid treatment using hydrochloric acid, sulfuric acid, etc., (b) alkali treatment using NaOH, KOH, N₂H₃, 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 a halogen atom or an anion derived from an inorganic acid, and (d) organic treatment using alcohols, hydrocarbon compounds, formamide, aniline, etc. These treatments may be performed individually or in combination of two or more treatments.

[0092] The particle properties of the layered silicate can be controlled by grinding, granulation, particle separation, fractionation, etc., at any point before, during, or after any of the processes. The method can be any purposeful method. In particular, examples of granulation methods include spray granulation, tumbling granulation, compression granulation, agitation granulation, briquetting, compacting, extrusion granulation, fluid bed granulation, emulsification granulation, and liquid granulation. Of the above, spray granulation, tumbling granulation, and compression granulation are particularly preferred granulation methods.

[0093] The layered silicates described above can, of course, be used as is, but they can also be used in combination with organoaluminum compounds such as trimethylaluminum, triethylaluminum, tri-i-butylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, and di-i-butylaluminum hydride, as well as organoaluminum oxy compounds containing Al-O-Al bonds.

[0094] To support the catalytically active components (A) and (B) on a layered silicate, components (A) and (B) may be brought into contact with the layered silicate, or components (A) and (B), an organoaluminum compound or organoaluminum oxy compound, and a layered silicate may be brought into contact with each other. The method of contact between each component is not particularly limited, and for example, the following methods can be arbitrarily adopted. Method (6): Components (A) and (B) are brought into contact with an organoaluminum compound or organoaluminum oxy compound, and then brought into contact with a layered silicate carrier. Method (7): After bringing components (A) and (B) into contact with a layered silicate carrier, the carrier is brought into contact with an organoaluminum compound or an organoaluminum oxy compound. Method(8): After bringing an organoaluminum compound or organoaluminum oxy compound into contact with a layered silicate support, it is brought into contact with component (A) and component (B).

[0095] Of these contact methods, methods (6) and (8) are preferred. In any of the contact methods, the components are typically brought into contact with each other under stirring or without stirring in an inert atmosphere such as nitrogen or argon, in the presence of liquid inert hydrocarbons such as aromatic hydrocarbons (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene, and ethylbenzene, and aliphatic or alicyclic hydrocarbons (usually having 5 to 12 carbon atoms) such as n-heptane, n-hexane, n-decane, n-dodecane, and cyclohexane. When supporting components (A) and (B) on a layered silicate, the methods for supporting, solvent washing, and solvent removal can be the same as those for the inorganic support described above.

[0096] The proportions of catalytically active components (A) and (B), organoaluminum compounds or organoaluminum oxy compounds, and layered silicate carriers are not particularly limited, but the following ranges are preferred. The amount of component (A) and component (B) supported is such that, per gram of layered silicate carrier, the total amount of transition metal (M) contained in component (A) and component (B) 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. Furthermore, when using organoaluminum compounds or organoaluminum oxy compounds, the molar ratio (Al / M) of aluminum atoms contained in the organoaluminum compound or organoaluminum oxy compound to the total amount of transition metal (M) contained in component (A) and component (B) is preferably in the range of 0.01 to 100, more preferably 0.1 to 50, and even more preferably 0.2 to 10.

[0097] The olefin polymerization catalyst thus obtained may undergo prepolymerization in or outside the polymerization tank in the presence of an olefin. An olefin is a hydrocarbon containing at least one carbon-carbon double bond, and examples include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, and divinylbenzene, but there are no particular restrictions on the type, and mixtures of these with other olefins may be used. Ethylene and propylene are preferred. More preferably ethylene.

[0098] The method of supplying olefins during prepolymerization can be any method, such as supplying the olefins to the reaction vessel at a constant rate or under constant pressure, a combination of these methods, or by introducing stepwise changes. The pre-polymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours. Furthermore, the amount of prepolymerization is preferably 0.01 to 100 parts by weight, and more preferably 0.1 to 50 parts by weight, of the prepolymerized polymer per 1 part by weight of the polyolefin polymerization catalyst. After prepolymerization is complete, the catalyst can be used as is, depending on its intended use, but drying may be performed if necessary.

[0099] 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. By keeping the reaction rate within this range, it is believed that the activation reaction will be promoted without causing a decrease in the reaction rate. Furthermore, it is thought that the dissolution of the prepolymerization polymer, deterioration of particle shape caused by an excessively fast prepolymerization rate, and deactivation of active sites due to side reactions can be suppressed.

[0100] Prepolymerization can and is preferable to be carried out in a liquid such as an organic solvent. 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. Higher concentrations lead to increased activation of components (A) and (B), resulting in a highly active catalyst.

[0101] Furthermore, it is possible to include polymers such as polyethylene, polypropylene, and polystyrene, as well as inorganic oxide solids such as silica and titania, in the contact mixture during or after the contact between the olefin polymerization catalyst and the olefin.

[0102] The catalyst may be dried after prepolymerization. There are no particular restrictions on the drying method, but examples include drying under reduced pressure, heating, and drying by circulating a drying gas. These methods may be used individually or in combination of two or more methods. During the drying process, the catalyst may be stirred, vibrated, or allowed to flow, or it may be left to stand. The olefin polymerization catalyst of the present invention may be used after prepolymerization, or it may be used before prepolymerization.

[0103] II. Method for producing ethylene polymers The present invention provides a method for producing an ethylene-based polymer, characterized by polymerizing ethylene, or ethylene and an α-olefin having 3 to 10 carbon atoms, in the presence of the olefin polymerization catalyst of the present invention described above. In the method for producing ethylene polymers of the present invention, by using the olefin polymerization catalyst of the present invention described above, an ethylene polymer with an excellent balance of moldability, strength, and durability can be obtained.

[0104] In the method for producing ethylene-based polymers of the present invention, the monomer used may be ethylene alone, or a combination of ethylene and an α-olefin having 3 to 10 carbon atoms. Examples of α-olefins having 3 to 10 carbon atoms include propylene, 1-butene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl-1,7-octadiene, cyclopentene, norbornene, and ethylidenenorbornene. Preferably, α-olefins having 3 to 8 carbon atoms are used, and more preferably, α-olefins having 4 to 6 carbon atoms.

[0105] Any polymerization method can be employed as long as the catalyst component and each monomer come into efficient contact. Specifically, slurry polymerization using an inert solvent, bulk polymerization using propylene as the solvent without substantially using an inert solvent, solution polymerization, or gas-phase polymerization that keeps each monomer in gaseous form without substantially using a liquid solvent can be employed. In addition, methods involving continuous polymerization, batch polymerization, or prepolymerization can also be applied. Among these, slurry polymerization is preferred in terms of controlling the properties of polymer particles. Furthermore, a multi-stage polymerization method is also applicable, in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, and polymerization temperature are different for two or more stages. In slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as isobutane, hexane, heptane, pentane, cyclohexane, benzene, and toluene, either alone or in mixtures, are used as polymerization solvents. The polymerization temperature is 0°C to 150°C, and hydrogen can be used as an auxiliary molecular weight modifier. The polymerization pressure is suitable at 0 MPa to 200 MPa, preferably 0 MPa to 6 MPa. In the case of copolymerization, the quantitative ratio of each monomer in the reaction system does not need to be constant over time. It is convenient to supply each monomer at a constant mixing ratio, and it is also possible to change the mixing ratio of the supplied monomers over time. Further, any of the monomers may be added in portions in consideration of the copolymerization reaction ratio.

[0106] Generally, when polymerizing an ethylene-based polymer, an antistatic agent such as Stadis (product name) or STATSAFE (product name) manufactured by Innospec (agent: Maruwa Bussan) may be used to suppress electrostatic adhesion of the polymer to the polymerization reactor. The antistatic agent such as Stadis or STATSAFE, which has been diluted in an inert hydrocarbon medium, may also be added to the polymerization reactor via a pump or the like. Addition methods include a method of adding the antistatic agent to the olefin polymerization catalyst in advance, and a method of adding the antistatic agent to the polymerization reactor. Regarding the addition amount, in the case of slurry polymerization, the amount is preferably 0.1 ppm to 500 ppm relative to the solvent, and more preferably 1 ppm to 50 ppm. Further, in the case of a gas phase method, the amount is preferably 1 ppm to 500 ppm, and more preferably 10 ppm to 100 ppm, relative to the production amount of the ethylene-based polymer per unit time.

[0107] The molecular weight of the produced polymer can be adjusted by changing the polymerization temperature or adding hydrogen into the polymerization reactor, and a method of adjusting the molecular weight by adding hydrogen is preferably used. Hydrogen is inserted into the bond between the transition metal and the polymer chain to cause a chain transfer reaction, and the polymer chain is eliminated from the transition metal, thereby stopping the growth reaction and preventing the molecular weight from further increasing. Therefore, increasing the hydrogen addition amount to raise the hydrogen concentration in the reactor results in a lower molecular weight, while decreasing the hydrogen addition amount to lower the hydrogen concentration results in a higher molecular weight. The likelihood of this chain transfer reaction caused by hydrogen varies depending on the type, content ratio and the like of the transition metal compound contained in the olefin polymerization catalyst.

[0108] A catalyst for olefin polymerization containing only component (A) as a transition metal compound is suitable for producing polymers containing relatively small amounts of macromonomers. On the other hand, a catalyst for olefin polymerization containing only component (B) as a transition metal compound is suitable for copolymerizing α-olefins and macromonomers while also producing macromonomers itself, thereby producing high molecular weight copolymers with branched structures. Furthermore, a combination of components (A) and (B) is preferable, as component (B) exhibits higher copolymerization reactivity with α-olefins (comonomers) having 3 to 10 carbon atoms than component (A). In the present invention, the catalyst for olefin polymerization includes a component (A) that generates relatively low molecular weight macromonomers at a relatively low frequency, and a component (B) that copolymerizes macromonomers derived from component (A) and generates a (co)polymer with a higher molecular weight than component (A), and is less likely to polymerize the relatively high molecular weight macromonomers it generates, as a transition metal compound. This combination makes it possible to produce ethylene-based polymers with a broad molecular weight distribution while suppressing the generation of an excess number of high molecular weight long-chain branches. Furthermore, the shape of the molecular weight distribution, that is, whether there is a large proportion of low molecular weight polymer components or a large proportion of high molecular weight polymers, can be controlled by changing the amounts of component (A) and component (B).

[0109] In polymerization, in addition to using a single reactor, a multi-stage polymerization method using multiple reactors is also employed. This involves connecting reactors with the same or different reaction conditions, and continuously or intermittently supplying the polymer produced in the first reactor to the second reactor with or without a solvent, and continuing polymer production under the reaction conditions of the second reactor. There are no restrictions on the number of reactors, but preferably two or three reactors are used. By changing various conditions such as polymerization temperature, polymerization pressure, monomer concentration, comonomer concentration, and hydrogen concentration between the reaction conditions of the first reactor and the subsequent reactors, a mixture of polymers produced in each reactor can be obtained. By changing the hydrogen concentration, it is possible to broaden the molecular weight distribution, and by changing the comonomer concentration in addition to the hydrogen concentration, it becomes possible to produce polymers with different comonomer content for each molecular weight. Furthermore, by changing the monomer concentration and polymerization temperature to change the amount of polymer produced in each reactor, it is also possible to control the ratio of polymers produced in each reactor. In multi-stage polymerization, a different or the same olefin polymerization catalyst may be added to the second and subsequent stages, and a device for removing unreacted gases between reactor connections may be provided.

[0110] Furthermore, components for removing moisture, so-called scavengers, may be added to the polymerization system. Suitable scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum, and tri-i-butylaluminum; the aforementioned organoaluminum oxy compounds; modified organoaluminum compounds containing branched alkyl groups; organozinc compounds such as diethylzinc and dibutylzinc; organomagnesium compounds such as diethylmagnesium, dibutylmagnesium, and ethylbutylmagnesium; and greenya compounds such as ethylmagnesium chloride and butylmagnesium chloride. Among these, triethylaluminum, tri-i-butylaluminum, and ethylbutylmagnesium are preferred, with triethylaluminum being particularly preferred.

[0111] III. Physical properties of the resulting ethylene polymer Ethylene-based polymers obtained by polymerizing ethylene, or ethylene and α-olefins having 3 to 10 carbon atoms, in the presence of the olefin polymerization catalyst of the present invention not only have high melt tension and excellent moldability, but also high strength and durability. The ethylene-based polymers obtained in this way have an excellent balance of moldability, strength, and durability. Ethylene-based polymers obtained using the olefin polymerization catalyst of the present invention are suitably used as plastic molding materials, and are particularly suitably used as plastic molding materials for hollow containers. Furthermore, the ethylene-based polymer produced using the olefin polymerization catalyst of the present invention may be used in combination with other polymers. In addition, the ethylene-based polymer may be used after being mixed with various additives and then melt-kneaded.

[0112] In the present invention, an ethylene-based copolymer having the following physical properties and suitable for hollow containers is obtained. (1) MFR (190℃, 2.16kg load) The melt flow rate of the ethylene-based polymer obtained in the present invention, i.e., the MFR (at 190°C and a 2.16 kg load), may be 0.001 g / 10 min to 1000 g / 10 min, 0.005 g / 10 min to 200 g / 10 min, 0.01 g / 10 min to 50 g / 10 min, 0.02 g / 10 min to 5.0 g / 10 min, and most preferably 0.10 g / 10 min to 1.0 g / 10 min. Because the MFR (Metal Flow Rate) falls within the above range, it is easier to reduce the load on the extruder motor during molding and suppress the increase in resin heat generation due to shearing. This suppresses the occurrence of flow instability phenomena such as shark skin and melt fracture, and maintains a good appearance of the molded product. It also results in good drop impact resistance and long-term durability of the molded product.

[0113] (2) HLMFR (190℃, 21.6kg load) The high-load melt flow rate (HLMFR) of the ethylene-based polymer obtained in the present invention, i.e., HLMFR (190°C, 21.6 kg load), may be 0.01 g / 10 min to 1000 g / 10 min, 0.1 g / 10 min to 500 g / 10 min, 1.0 g / 10 min to 300 g / 10 min, 2.0 g / 10 min to 200 g / 10 min, and most preferably 40 g / 10 min to 60 g / 10 min. Since HLMFR falls within the above range, it is expected to exhibit similar performance to MFR as described in (1). MFRs and HLMFRs can be adjusted primarily by controlling the amount of hydrogen and the polymerization temperature during the polymerization of ethylene-based polymers. In addition, we believe they can also be altered by changing the ratio of component (A) and component (B) when producing the catalyst for olefin polymerization.

[0114] (3) Density The density of the ethylene polymer obtained in this invention is 0.850 g / cm³. 3 ~0.980g / cm 3 It is acceptable for it to be 0.935 g / cm³. 3 ~0.970g / cm 3 It may be such, and more preferably 0.945 g / cm³ 3 ~0.965g / cm 3 That is the case. When the density falls within the above range, the environmental stress crack resistance and rigidity are good. The density can be controlled by the amount of α-olefin used when polymerization is carried out using conventionally well-known catalysts, mainly for olefin polymerization. In addition, it is thought that the density can also be changed by the ratio of component (A) and component (B) when manufacturing the olefin polymerization catalyst.

[0115] (4) Bulk density The bulk density of the ethylene polymer obtained in this invention is 0.20 g / cm³. 3 ~0.50g / cm 3 It is acceptable for it to be 0.30 g / cm³. 3 ~0.50g / cm 3 It may be such, and more preferably 0.35 g / cm³ 3~0.45g / cm 3 That is the case. When the bulk density is within the above range, it leads to improved polymer productivity and increased stability in the transfer process of the resulting ethylene-based polymer. The bulk density can be adjusted mainly by the properties of component (D), the method of producing the catalyst, and the suppression of aggregation between polyethylene particles in the polymerization reactor by adding an antistatic agent.

[0116] (5) Molecular weight distribution (Mw / Mn) The molecular weight distribution (Mw / Mn) of the ethylene polymer obtained in the present invention may be 6.0 to 60, 8.0 to 50, 10 to 40, or 10 to 30, and is most preferably 12 to 20. When the molecular weight distribution falls within the above range, flow instability phenomena such as sharkskin are less likely to occur, and furthermore, melt tension is good, as well as compatibility and impact resistance. By broadening the molecular weight distribution within a suitable range, it becomes suitable for FNCT and melt tension tests, and it becomes easier to ensure tensile impact strength without an excessive amount of low molecular weight components. In this invention, the molecular weight distribution (Mw / Mn) is calculated from the weight-average molecular weight (Mw) and number-average molecular weight (Mn) measured by gel permeation chromatography (GPC). The molecular weight distribution can be adjusted primarily by the ratio of components (A) and (B), and in multi-stage polymerization, by reacting at each stage under different polymerization conditions.

[0117] (6) Melt tension (MT) The melt tension (MT) of the ethylene polymer obtained in the present invention is preferably 50 mN or more, more preferably 60 mN or more, and even more preferably 70 mN or more, at a measurement temperature of 190°C. Melt tension can be controlled by MFR and HLMFR. It can also be adjusted by the molecular weight distribution. Reducing MFR or HLMFR increases melt tension, and widening the molecular weight distribution also increases melt tension. Furthermore, melt tension is affected by long-chain branching; the more long-chain branching there is, the higher the melt tension. When the melt tension is within the above range, drawdown resistance is good and molding becomes easier.

[0118] (7) Tensile impact strength (TIS) The tensile impact strength (TIS) of the ethylene-based polymer obtained in the present invention is preferably 130 kJ / m². 2 The above is more preferable, 150 kJ / m³ 2 The above is preferable, and more preferably 170 kJ / m 2 The above is preferable, and more preferably 200 kJ / m 2 That's all. In this invention, the tensile impact strength (TIS) is measured using a test specimen with the shape of ASTM D1822 Type-S, in accordance with Method B of JIS K 7160-1996. Tensile impact strength (TIS) can be controlled by weight-average molecular weight, molecular weight distribution, and density. Increasing molecular weight, narrowing molecular weight distribution, and decreasing density leads to higher impact strength, but this comes at the cost of poor moldability.

[0119] (8) Environmental stress cracking resistance The ethylene polymer obtained in the present invention has a fracture time of preferably 100 hours or more, more preferably 200 hours or more, even more preferably 600 hours or more, and even more preferably 1000 hours or more in a full-circumference notch creep test (FNCT) conducted in accordance with ISO 16770. Environmental stress cracking resistance (FNCT) can be controlled by weight average molecular weight, molecular weight distribution, and density. Increasing the molecular weight and decreasing the density lead to improved environmental stress cracking resistance (FNCT), but this is on the other hand in a trade-off relationship with moldability. Therefore, in order to increase the rupture time in FNCT while achieving compatibility with moldability, it is mentioned that control is performed to obtain a high-molecular-weight polymer having a moderately broadened molecular weight distribution while suppressing the generation of an excessive number of high-molecular-weight long-chain branches that lead to increased viscosity. Examples

[0120] The present invention will be described in further detail with reference to the following examples and comparative examples, but the present invention is not limited thereto. In the examples, the following evaluation methods were performed. All catalyst synthesis steps and polymerization steps were carried out under a purified nitrogen atmosphere, and the solvents used were dehydrated and purified with Molecular Sieve 4A (trade name, manufactured by Union Showa K.K.).

[0121] 1. Evaluation Methods (1) MFR (190°C, 2.16 kg load) MFR was measured in accordance with JIS K6760 under the conditions of a temperature of 190°C and a load of 2.16 kg. (2) HLMFR (190°C, 21.6 kg load) HLMFR was measured in accordance with JIS K6922-2:1997 under the conditions of a temperature of 190°C and a load of 21.6 kg. (3) Density Density was measured in accordance with JIS K6922-1,2:1997. (4) Bulk Density In accordance with the method described in JIS K6730, the obtained ethylene-based polymer was freely dropped using a funnel, collected in a container of known volume, then the weight of the polymer in the container was measured, and the weight (g) of the ethylene-based polymer per 1 ml was taken as the bulk density.

[0122] (5) Molecular Weight Distribution (Mw / Mn) Gel permeation chromatography (GPC) was performed under the following conditions, and the number-average molecular weight (Mn) and weight-average molecular weight (Mw) were measured by converting the retention volume to molecular weight, and the molecular weight distribution (Mw / Mn) was calculated. [GPC equipment, measurement conditions] Equipment: Waters GPC (ALC / GPC 150C) Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm) Columns: Showa Denko AD806M / S (3 pieces) 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 approximately 1 hour to prepare a sample solution with a concentration of 1 mg / mL. [Conversion from holding capacity to molecular weight] The conversion from holding capacity to molecular weight was performed using a calibration curve prepared in advance using standard polystyrene. The standard polystyrene used was the following brands manufactured by Tosoh Corporation: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, and A1000. Calibration curves were created by injecting 0.2 mL of a solution of each standard polystyrene dissolved in ODCB (containing 0.5 mg / mL of BHT) so that the concentration of each standard polystyrene was 0.5 mg / mL. The calibration curves were approximated using a cubic equation obtained by the least squares method. The viscosity formula [η] = K × Mα used for conversion to molecular weight was calculated using 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

[0123] (6) Melt tension (MT) The stress was determined by measuring the stress when a molten ethylene-based polymer was stretched at a constant rate, and the measurement was performed under the following conditions. [Measurement conditions] Equipment used: Capillograph 1B, manufactured by Toyo Seiki Seisakusho. Nozzle diameter: 2.095mm Nozzle length: 8.0mm Inflow angle: 180°(flat) Extrusion speed: 15 mm / min Pickup speed: 6.5m / min Measurement temperature: 190℃

[0124] (7) Tensile impact strength (TIS) [Method for preparing tensile impact strength test samples] The sample was placed in a 1 mm thick heat press mold and preheated in a hot press machine at a surface temperature of 230°C for 5 minutes. Then, the sample was melted and residual gases were removed by repeatedly applying and removing pressure. Further pressurization was applied at 4.9 MPa and held for 5 minutes. After that, the sample was gradually cooled at a rate of 10°C / min while maintaining the 4.9 MPa pressure, and the molded plate was removed from the mold when the temperature had dropped to near room temperature. The resulting molded plate was conditioned for more than 48 hours in an environment of 23 ± 2°C and 50 ± 5°C humidity. Test specimens in the shape of ASTM D1822 Type-S were punched out from the conditioned press plate and used as tensile impact strength test samples. [Tensile Impact Strength Test Conditions (TIS)] The tensile impact strength was measured using the above-mentioned test specimens in accordance with Method B of JIS K 7160-1996. The only difference from JIS K 7160-1996 was the shape of the test specimens. Other measurement conditions were tested in accordance with JIS K 7160-1996.

[0125] (8) Environmental stress cracking resistance (FNCT) A full-circumference notch creep test (FNCT) was performed in accordance with ISO 16770. The specimen was prepared as a rectangular prism measuring 6 mm x 6 mm x 11 mm, with 1 mm notches made around its entire circumference using a razor blade, resulting in a test piece with 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 fractured was measured and defined as the fracture time for FNCT.

[0126] (9) Viscoelasticity Viscoelasticity tests were performed using MCR302 from Anton Paar under the following conditions. [Viscoelasticity measurement conditions] • Test specimens: A 1mm thick pressed sheet was created by pressing at a temperature of 180°C, cut to an appropriate size, and measured. • Fixture used: 25φ parallel plate ·Measurement temperature: 170℃ Distortion: 1-10% • Frequency: 100~0.01 rad / sec

[0127] 2. Preparation of components (A) and (B) Bis(n-butylcyclopentadienyl)zirconium dichloride (hereinafter referred to as metallocene A1) was obtained from Fujifilm Wako Pure Chemical Industries, Ltd.

[0128] [Synthesis Example 1] Synthesis of racemi-dimethylsilylenebis{(2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indenyl)}zirconium dichloride (hereinafter referred to as metallocene B1): Metallocene B1 is a compound represented by formula (2) above. Following the procedure described in Synthesis Example 1 of Japanese Patent Publication No. 2012-149160, the ligand was synthesized, and the complex was synthesized in the same manner except that zirconium tetrachloride (13 mmol) was used instead of hafnium tetrachloride (13 mmol) to obtain metallocene B1.

[0129] [Synthesis Example 2] Synthesis of racemi-dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride (hereinafter referred to as metallocene B2): Metallocene B2 was synthesized according to the procedure described in Organometallics, 1994, vol. 13, pp. 954-963.

[0130] 3. Catalyst preparation and production of ethylene polymers [Example 1] (1) Preparation of solid catalyst As component (D), 3.5 g of silica gel, which was prepared by calcining uncalcined Grace's Sylopol 2212 at 400°C for 7 hours, was mixed with 86 ml of toluene and formed into a slurry at room temperature. Separately from the above process, 28 mg (69 μmol) of metallocene A1 as component (A) and 15 mg (18 μmol) of metallocene B1 as component (B) were weighed into a container, to which 18 ml of toluene and 9.5 ml of methylaluminoxane toluene solution (purchased from Albemarle Co., Ltd.; MAO concentration 20 wt%) (29 mmol as aluminum) were added as component (C), and the mixture was stirred at room temperature for 1 hour. This solution was added to a toluene slurry of silica gel, which is component (D), and stirred at 40°C for 1 hour. The total amount of metallocene A1 and metallocene B1 per gram of silica gel was 25 μmol / g. After stopping the stirring, the supernatant was removed, and the catalyst was washed by adding 200 ml of hexane and removing the supernatant twice. The solvent was removed under reduced pressure to obtain a free-flowing solid catalyst (MIX-1).

[0131] (2) Ethylene / 1-hexene copolymerization In a 2-liter stainless steel autoclave equipped with stirring and temperature control devices, under nitrogen, 1.0 mmol of triisobutylaluminum, 1 ml of 1-hexene, 1 ml of Statsafe6000 (product name of Innospec) diluted to 2 vol% with hexane as a reactor fouling inhibitor, and 800 ml of purified isobutane were added, and the temperature was raised to 70°C while stirring. Next, 38 ml (1.7 mmol) of hydrogen was introduced, followed by the introduction of ethylene until the partial pressure reached 1 MPa. At this time, the molar ratio of hydrogen to ethylene in the gas phase inside the autoclave was 0.24 mol%. Subsequently, 45 mg of the above solid catalyst (MIX-1) was injected under pressure with nitrogen gas, and polymerization was carried out for 90 minutes. During polymerization, the temperature was controlled to maintain 70°C, and ethylene was continuously supplied to keep the total pressure constant. 1-hexene and hydrogen were supplied in proportion to the rate of ethylene consumption. The molar ratio of hydrogen to ethylene in the gas phase inside the autoclave at the end of polymerization was 0.15 mol%. Additionally, 1.5 ml of 1-hexene was added during polymerization. As a result of polymerization, 186 g of a free-flowing ethylene-based polymer was obtained. The polymerization results and physical property measurement results are summarized in Table 1. The GPC chart of the obtained ethylene-based polymer is shown in Figure 1.

[0132] [Comparative Example 1] (1) Preparation of solid catalyst Solid catalyst (MIX-2) was prepared in the same manner as in Example 1, except that metallocene A1 was changed from 28 mg (69 μmol) to 21 mg (53 μmol) and metallocene B2 was changed from 15 mg (18 μmol) to 22 mg (35 μmol). (2) Ethylene / 1-hexene copolymerization In the ethylene / 1-hexene copolymerization of Example 1, 53 mg of the above-mentioned solid catalyst (MIX-2) was used instead of 45 mg of solid catalyst (MIX-1) as the solid catalyst, and the polymerization time was changed from 90 minutes to 60 minutes. The polymerization was carried out in the same manner as in Example 1. The molar ratio of hydrogen to ethylene in the gas phase inside the autoclave before the start of polymerization was 0.19 mol%, and the molar ratio of hydrogen to ethylene in the gas phase inside the autoclave at the end of polymerization was 0.11 mol%. In addition, 1 ml of hexene was added during polymerization. As a result of polymerization, 130 g of a free-flowing ethylene-based polymer was obtained. The polymerization results and physical property measurement results are summarized in Table 1. The GPC chart of the obtained ethylene-based polymer is shown in Figure 1.

[0133] [Comparative Example 2] Table 1 summarizes the results of physical property measurements for Novatec HD HB431 (manufactured by Nippon Polyethylene Co., Ltd.).

[0134] [Comparative Example 3] Table 1 summarizes the results of physical property measurements for Evolu H SP6505 (a polymer obtained from a multi-stage slurry polymerization process using a metallocene catalyst, manufactured by Prime Polymer Co., Ltd.).

[0135] [Table 1]

[0136] 4. Discussion Comparing the melt tension (MT), tensile impact strength (TIS), and FNCT fracture time of Example 1 and Comparative Examples 1-3 shown in Table 1, the ethylene polymer of Example 1 exhibited excellent performance in all of these areas, demonstrating that it is an ethylene polymer with an excellent balance of moldability, strength, and durability. In particular, the FNCT fracture time of the ethylene polymer of Example 1 was significantly longer, indicating a substantial improvement in durability compared to conventional ethylene polymers. Although the ethylene polymer in Comparative Example 1 had a high MT, its TIS and FNCT were inferior to those of the example. The ethylene-based polymer in Comparative Example 2 was inferior to the example in all aspects: MT, TIS, and FNCT. Although the ethylene-based polymer in Comparative Example 3 had a high TIS, its MT and FNCT were inferior to those of the example.

[0137] Furthermore, as shown in Table 1, the HLMFRs of the ethylene polymer in Example 1 and the ethylene polymer in Comparative Example 1 are almost equivalent. However, as is clear from the GPC charts of the ethylene polymers in Example 1 and Comparative Example 1 shown in Figure 1, the ethylene polymer in Example 1 had slightly more high molecular weight components and slightly less low molecular weight components than the ethylene polymer in Comparative Example 1. Thus, we believe that the ethylene polymer in Example 1 has a higher FNCT than Comparative Example 1 because it contains a sufficient amount of high molecular weight components even when the HLMFR is adjusted to improve fluidity. Moreover, since metallocene B2 used in Comparative Example 1 copolymerizes more easily with high molecular weight macromonomers than metallocene B1 used in Example 1, Comparative Example 1 has a higher proportion of high molecular weight long-chain branched polymers. Therefore, even if the weight-average molecular weight is the same, the viscosity tends to be higher, and when comparing ethylene polymers with HLMFRs adjusted to the desired range, the amount of low molecular weight components increases, leading to a decrease in strength.

[0138] [Reference example 1] (1) Preparation of a solid catalyst using only metallocene B1 Solid catalyst (SC-1) was obtained by preparing the solid catalyst in the same manner as in Example 1, except that metallocene A1 was not used and the amount of metallocene B1 was 74 mg (88 μmol). (2) Ethylene / 1-hexene copolymerization In a 2-liter stainless steel autoclave equipped with stirring and temperature control devices, under nitrogen, 1.0 mmol of triisobutylaluminum, 6 ml of 1-hexene, 1 ml of Statsafe6000 (product name of Innospec) diluted to 2 vol% with hexane as a reactor fouling inhibitor, and 800 ml of purified isobutane were added, and the temperature was raised to 70°C while stirring. Next, 25 ml (1.1 mmol) of hydrogen was introduced, followed by the introduction of ethylene until the partial pressure reached 1 MPa. At this time, the molar ratio of hydrogen to ethylene in the gas phase inside the autoclave was 0.14 mol%. Subsequently, 25 mg of the above solid catalyst (SC-1) was injected under pressure with nitrogen gas, and polymerization was carried out for 60 minutes. During polymerization, the temperature was controlled to maintain 70°C, and ethylene was continuously supplied to keep the total pressure constant. 1-hexene and hydrogen were supplied in proportion to the rate of ethylene consumption. The molar ratio of hydrogen to ethylene in the gas phase inside the autoclave at the end of polymerization was 0.16 mol%. Additionally, 7 ml of 1-hexene was added during polymerization. As a result of polymerization, 176 g of a free-flowing ethylene-based polymer was obtained. The polymerization results and physical property measurement results are summarized in Table 2. The GPC chart of the obtained ethylene-based polymer is shown in Figure 2.

[0139] (3) Production of low molecular weight polyethylene for blending Low molecular weight polyethylene for blending with an MFR of 46 g / 10 min was produced by polymerizing ethylene at 80°C using a 290 L liquid-filled loop reactor with dehydrated purified isobutane, triisobutylaluminum, and the Ziegler-Natta prepolymerization catalyst described in Comparative Example B1 of Japanese Patent Application Publication No. 2012-72229, by continuously supplying hydrogen and ethylene. (4) Preparation of blended products In a 300 ml Erlenmeyer flask, 180 ml of xylene, 1.6 g of the ethylene polymer obtained in (2) above, 2.4 g of the low molecular weight polyethylene obtained in (3) above, and 1.0 to 1.5 g of 2,6-di-t-butylhydroxytoluene (BTH) were added. This mixture was stirred at 125 to 130 °C for 45 to 90 minutes to obtain a xylene solution in which the ethylene polymer and low molecular weight polyethylene were completely dissolved in the xylene. The xylene solution was poured into 500 mL of ethanol to precipitate the ethylene polymer and low molecular weight polyethylene. The ethylene polymer and low molecular weight polyethylene recovered by filtration were vacuum-dried at 80 °C to obtain a blend of the ethylene polymer and low molecular weight polyethylene. The viscoelasticity of the blend was measured, and the results are shown in Figure 3.

[0140] [Reference example 2] (1) Preparation of a solid catalyst using only metallocene B2 Solid catalyst (SC-2) was obtained by preparing the solid catalyst in the same manner as in Comparative Example 1, except that metallocene A1 was not used and the amount of metallocene B2 was 55 mg (88 μmol). (2) Ethylene / 1-hexene copolymerization Polymerization was carried out in the same manner as in Reference Example 1, except that 33 mg of the above-mentioned solid catalyst (SC-2) was used instead of 25 mg of solid catalyst (SC-1) in the ethylene / 1-hexene copolymerization. The molar ratio of hydrogen to ethylene in the gas phase inside the autoclave was 0.16 mol% before the start of polymerization and 0.21 mol% at the end of polymerization. 7 ml of 1-hexene was added during polymerization. As a result of polymerization, 176 g of a free-flowing ethylene-based polymer was obtained. The polymerization results and physical property measurement results are summarized in Table 2. The GPC chart of the obtained ethylene-based polymer is shown in Figure 2.

[0141] [Reference example 3] (1) Preparation of a solid catalyst using only metallocene B2 Solid catalyst (SC-2) was obtained by preparing the solid catalyst in the same manner as in Comparative Example 1, except that metallocene A1 was not used and the amount of metallocene B2 was 55 mg (88 μmol). (2) Ethylene / 1-hexene copolymerization In the ethylene / 1-hexene copolymerization of Reference Example 1, 33 mg of the above-mentioned solid catalyst (SC-2) was used instead of 25 mg of solid catalyst (SC-1), and the amount of hydrogen introduced was changed from 25 ml (1.1 mmol) to 75 ml (3.3 mmol). Polymerization was carried out in the same manner as in Reference Example 1. The molar ratio of hydrogen to ethylene in the gas phase inside the autoclave was 0.47 mol% before the start of polymerization and 0.42 mol% at the end of polymerization. 6 ml of 1-hexene was added during polymerization. The polymerization yielded 146 g of a free-flowing ethylene-based polymer. The polymerization results and physical property measurements are summarized in Table 2. The GPC chart of the obtained ethylene-based polymer is shown in Figure 2.

[0142] (3) Production of low molecular weight polyethylene for blending Low molecular weight polyethylene for blending was produced using the same procedure as in Reference Example 1 (3). (4) Preparation of blended products In preparing the blended product of Reference Example 1, the ethylene-based polymer obtained in Reference Example 3 (2) was used instead of the ethylene-based polymer obtained in Reference Example 1 (2), except that the blended product was prepared in the same manner as in Reference Example 1 (4). The viscoelasticity of the blended product was measured, and the results are shown in Figure 3.

[0143] [Table 2]

[0144] In Reference Examples 1 and 2, ethylene polymers were produced using only metallocene B1 or metallocene B2 as the transition metal compound under the same polymerization conditions. As shown in Figure 2, the molecular weight peaks of the ethylene polymers in Reference Example 1 and Reference Example 2 are almost the same, and although the ethylene polymer in Reference Example 2 has lower molecular weight components, as shown in Table 2, the HLMFR of the ethylene polymer in Reference Example 2 is smaller than that of the polymer in Reference Example 1. This suggests that the ethylene polymer in Reference Example 2 contains more high-viscosity polymers. In Reference Examples 1 and 3, ethylene polymers were produced by using only metallocene B1 or metallocene B2 as the transition metal compound, and adjusting the amount of hydrogen introduced so that the HLMFR was approximately the same. As shown in Table 2, the ethylene polymer of Reference Example 1 and the ethylene polymer of Reference Example 3 have almost equivalent HLMFRs. However, as is clear from the GPC charts of the ethylene polymers of Reference Example 1 and Reference Example 3 shown in Figure 2, the ethylene polymer of Reference Example 3 had more low molecular weight components than the ethylene polymer of Reference Example 1. Furthermore, as is clear from the viscoelasticity results of the blends of Reference Example 1 and Reference Example 3 shown in Figure 3, the viscosity of the blend of Reference Example 1 did not increase at low frequencies. The differences in molecular weight distribution and viscoelasticity of the polymers obtained in Reference Example 1 and Reference Example 3 are thought to be due to differences in the amount of long-term relaxation components. Specifically, Reference Example 1, which used metallocene B1, had a lower amount of long-term relaxation components in the resulting ethylene-based polymer compared to Reference Example 3, which used metallocene B2, and the blend in Reference Example 1 did not show an increase in viscosity at low frequencies. These long-term relaxation components are thought to originate from long-chain branching. In polymers produced when metallocene B1 or metallocene B2 is used alone as a catalytic active component in polymerization, the amount of long-chain branching is less when metallocene B1 is used than when metallocene B2 is used. This indicates that the catalytic properties (the amount of long-chain branching that can occur) differ between metallocene B1 and metallocene B2. [Industrial applicability]

[0145] The olefin polymerization catalyst of the present invention can be used to produce ethylene-based polymers with an excellent balance of moldability, strength, and durability. The ethylene-based polymer of the present invention, obtained in this manner, has an excellent balance of moldability, strength, and durability, and can be widely used as a plastic molding material.

Claims

1. A catalyst for olefin polymerization comprising the following components (A), (B), (C), and (D). Ingredient (A): Biscyclopentadienylzirconium dichloride, Bis(methylcyclopentadienyl)zirconium dichloride, Bis(n-propylcyclopentadienyl)zirconium dichloride, Bis(i-propylcyclopentadienyl)zirconium dichloride, Bis(n-butylcyclopentadienyl)zirconium dichloride, Bis(s-butylcyclopentadienyl)zirconium dichloride, Bis(t-butylcyclopentadienyl)zirconium dichloride, Bis(n-hexylcyclopentadienyl)zirconium dichloride, Bis(cyclohexylcyclopentadienyl)zirconium dichloride, Bis(1,3-dimethylcyclopentadienyl)zirconium dichloride, Bis(1,3-di-n-propylcyclopentadienyl)zirconium dichloride, Bis(1,3-di-i-propylcyclopentadienyl)zirconium dichloride, Bis(1,3-di-n-hexylcyclopentadienyl)zirconium dichloride, Bis(1,2-di-n-propylcyclopentadienyl)zirconium dichloride, Bis(1,2-di-i-propylcyclopentadienyl)zirconium dichloride, Bis(1,2,4-trimethylcyclopentadienyl)zirconium dichloride, Bis(pentamethylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-ethylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-n-propylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-i-propylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-i-butylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-s-butylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-t-butylcyclopentadienyl)zirconium dichloride, Bis(1-ethyl-3-n-propylcyclopentadienyl)zirconium dichloride, Bis(1-ethyl-3-i-propylcyclopentadienyl)zirconium dichloride, (Methylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride, (Methylcyclopentadienyl)(i-butylcyclopentadienyl)zirconium dichloride, (Methylcyclopentadienyl)(s-butylcyclopentadienyl)zirconium dichloride, (Methylcyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(i-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(s-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride, (i-propylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride, (i-Propylcyclopentadienyl)(i-Butylcyclopentadienyl)zirconium dichloride, (i-propylcyclopentadienyl)(s-butylcyclopentadienyl)zirconium dichloride, (i-propylcyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride, Bis(4-methoxybutylcyclopentadienyl)zirconium dichloride, Bis(butoxycyclopentadienyl)zirconium dichloride, Bis(butenylcyclopentadienyl)zirconium dichloride, Bis(trifluoromethylcyclopentadienyl)zirconium dichloride, Bis(trimethylsilylcyclopentadienyl)zirconium dichloride, Bis(phenylcyclopentadienyl)zirconium dichloride, and At least one metallocene compound selected from the group consisting of bis(n-butylcyclopentadienyl)hafnium dichloride Component (B): [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-(5-methyl-2-furyl)-4-(4-chlorophenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trifluoromethylphenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trimethylsilylphenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(1-naphthyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(2-naphthyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(2-phenanthuryl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(9-phenanthryl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(1-naphthyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-naphthyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-phenanthuryl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(9-phenanthuryl)-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-phenanthuryl)-indenyl}] zirconium dichloride, and, At least one metallocene compound selected from the group consisting of [1,1'-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(9-phenanthuryl)-indenyl}]zirconium dichloride Ingredient (C): Methylaluminoxane Component (D): Particulate carrier

2. The aforementioned component (B) is [1,1'-dimethylsilylenebis{2-(2-furyl)-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'-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-(5-methyl-2-furyl)-4-(4-chlorophenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trifluoromethylphenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trimethylsilylphenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(1-naphthyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(2-naphthyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(2-phenanthuryl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(9-phenanthryl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(1-naphthyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-naphthyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-phenanthuryl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(9-phenanthuryl)-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-phenanthuryl)-indenyl}] zirconium dichloride, and, The catalyst for olefin polymerization according to claim 1, which is at least one metallocene compound selected from the group consisting of [1,1'-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(9-phenanthuryl)-indenyl}]zirconium dichloride.

3. The aforementioned component (A) is bis(n-propylcyclopentadienyl)zirconium dichloride, Bis(i-propylcyclopentadienyl)zirconium dichloride, Bis(n-butylcyclopentadienyl)zirconium dichloride, Bis(s-butylcyclopentadienyl)zirconium dichloride, Bis(t-butylcyclopentadienyl)zirconium dichloride, Bis(n-hexylcyclopentadienyl)zirconium dichloride, Bis(cyclohexylcyclopentadienyl)zirconium dichloride, Bis(1,3-di-n-propylcyclopentadienyl)zirconium dichloride, Bis(1,3-di-i-propylcyclopentadienyl)zirconium dichloride, Bis(1,3-di-n-hexylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-n-propylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-i-propylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-i-butylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-s-butylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-t-butylcyclopentadienyl)zirconium dichloride, Bis(1-ethyl-3-n-propylcyclopentadienyl)zirconium dichloride, Bis(1-ethyl-3-i-propylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(i-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(s-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride, (i-propylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride, (i-Propylcyclopentadienyl)(i-Butylcyclopentadienyl)zirconium dichloride, (i-propylcyclopentadienyl)(s-butylcyclopentadienyl)zirconium dichloride, (i-propylcyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride, and The catalyst for olefin polymerization according to claim 1 or 2, which is at least one metallocene compound selected from the group consisting of bis(n-butylcyclopentadienyl)hafnium dichloride.

4. The aforementioned component (A) is bis(n-propylcyclopentadienyl)zirconium dichloride, Bis(i-propylcyclopentadienyl)zirconium dichloride, Bis(n-butylcyclopentadienyl)zirconium dichloride, Bis(s-butylcyclopentadienyl)zirconium dichloride, Bis(t-butylcyclopentadienyl)zirconium dichloride, Bis(n-hexylcyclopentadienyl)zirconium dichloride, Bis(cyclohexylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-n-propylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-i-propylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-i-butylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-s-butylcyclopentadienyl)zirconium dichloride, Bis(1-methyl-3-t-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(i-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(s-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride, (i-propylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride, (i-Propylcyclopentadienyl)(i-Butylcyclopentadienyl)zirconium dichloride, (i-propylcyclopentadienyl)(s-butylcyclopentadienyl)zirconium dichloride, (i-propylcyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride, and The catalyst for olefin polymerization according to claim 1 or 2, which is at least one metallocene compound selected from the group consisting of bis(n-butylcyclopentadienyl)hafnium dichloride.

5. The aforementioned component (A) is bis(n-propylcyclopentadienyl)zirconium dichloride, Bis(i-propylcyclopentadienyl)zirconium dichloride, Bis(n-butylcyclopentadienyl)zirconium dichloride, Bis(s-butylcyclopentadienyl)zirconium dichloride, Bis(t-butylcyclopentadienyl)zirconium dichloride, Bis(n-hexylcyclopentadienyl)zirconium dichloride, Bis(cyclohexylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(i-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(s-butylcyclopentadienyl)zirconium dichloride, (n-propylcyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride, (i-propylcyclopentadienyl)(n-butylcyclopentadienyl)zirconium dichloride, (i-Propylcyclopentadienyl)(i-Butylcyclopentadienyl)zirconium dichloride, (i-propylcyclopentadienyl)(s-butylcyclopentadienyl)zirconium dichloride, (i-propylcyclopentadienyl)(t-butylcyclopentadienyl)zirconium dichloride, and The catalyst for olefin polymerization according to claim 1 or 2, which is at least one metallocene compound selected from the group consisting of bis(n-butylcyclopentadienyl)hafnium dichloride.

6. The aforementioned component (B) is [1,1'-dimethylsilylenebis{2-(2-furyl)-4-phenyl-indenyl}]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-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-(5-methyl-2-furyl)-4-(4-chlorophenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-fluorophenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trifluoromethylphenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-trimethylsilylphenyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(1-naphthyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(2-naphthyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(2-phenanthuryl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(2-furyl)-4-(9-phenanthryl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(1-naphthyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-naphthyl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-phenanthuryl)-indenyl}] zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(9-phenanthuryl)-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-phenanthuryl)-indenyl}] zirconium dichloride, and, The catalyst for olefin polymerization according to claim 1 or 2, which is at least one metallocene compound selected from the group consisting of [1,1'-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(9-phenanthuryl)-indenyl}]zirconium dichloride.

7. The component (B) is [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-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- A catalyst for olefin polymerization according to claim 1 or 2, which is at least one metallocene compound selected from the group consisting of [furyl)-4-phenyl-indenyl]zirconium dichloride, [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl}]zirconium dichloride, and [1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)-indenyl}]zirconium dichloride.

8. A method for producing an ethylene-based polymer, comprising polymerizing ethylene, or ethylene and an α-olefin having 3 to 10 carbon atoms, in the presence of the olefin polymerization catalyst described in claim 1 or 2.

9. A method for producing an ethylene polymer according to claim 8, carried out by slurry polymerization.

Images