Transition metal compounds, catalysts for olefin polymerization, and methods for producing olefin polymers.

Abstract

To provide transition metal compounds as components of olefinic polymerization catalysts that enable production, with high catalytic activity, of ethylenic polymers having many long chain branches introduced thereinto and having high molecular weights.SOLUTION: The invention provides transition metal compounds [A] represented by the general formula [1] in the figure. (In the formula, M is a transition metal atom of Group 4 of the periodic table; n is an integer from 1 to 4; X is H, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating through a lone electron pair; Q is an atom of Group 14 of the periodic table; and R1 to R14 are each independently H, a C1-40 hydrocarbon group, or the like.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a transition metal compound, a catalyst for olefin polymerization, and a method for producing olefin polymers using the same. [Background technology]

[0002] Olefin polymers are molded using various molding methods and are used in a wide range of applications. For example, extruded ethylene polymers are used in films or sheets used for packaging food products, liquids, or daily necessities. The properties required of olefin polymers vary depending on the molding method or application, but for example, when performing T-die molding, it is required that the polymer can be molded stably even at high speeds (high-speed film formation processability) and has small neck-in properties.

[0003] Low-density polyethylene (LDPE), produced by high-pressure radical polymerization, has a complex long-chain branched structure, resulting in high melt tension and good moldability, such as a small neck-in, making it suitable for a variety of applications. However, it still suffers from problems such as low mechanical strength, including tensile strength, tear strength, and impact strength of molded articles, and poor high-speed film formation in T-die molding.

[0004] On the other hand, ethylene polymers produced using Ziegler catalysts or metallocene catalysts, in contrast to LDPE, have high tensile strength, tear strength, or impact strength due to their molecular structure, and are therefore used in applications where mechanical strength is required. However, they have problems such as low melt tension and poor moldability.

[0005] To solve these problems, a method has been proposed (Patent Documents 1 and 2, etc.) for producing long-chain branched ethylene polymers in the presence of a solid catalyst component consisting of two transition metal compounds and a solid support. Furthermore, methods for producing long-chain branched ethylene polymers in the presence of a solid catalyst component consisting of one type of transition metal compound and a solid support have been reported, including a method using a cross-linked bis(1-indenyl) type compound as the transition metal compound (e.g., Patent Document 3) and a method using a cross-linked cyclopentadienyl(1-indenyl) type compound (e.g., Patent Documents 4 and 5). On the other hand, Patent Document 6 reports olefin polymerization using a transition metal compound having a 2-indenyl group, as described later. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2006-233208 [Patent Document 2] Japanese Patent Publication No. 2009-144148 [Patent Document 3] Japanese Patent Publication No. 2019-059933 [Patent Document 4] Japanese Patent Publication No. 2019-059723 [Patent Document 5] Japanese Patent Publication No. 2019-059724 [Patent Document 6] Japanese Patent Publication No. 2020-050614 [Overview of the project] [Problems that the invention aims to solve]

[0007] Incidentally, it is desirable for the olefin polymerization catalyst used in the manufacturing process to have high catalytic activity from the viewpoint of manufacturing efficiency. Furthermore, when olefin polymers, such as ethylene polymers, are used in applications requiring high strength, such as pipes, it is desirable for the olefin polymer to have a high molecular weight. However, the technologies reported in Patent Documents 3 to 6, etc., had problems such as low catalytic activity of the olefin polymerization catalyst used in the manufacturing of olefin polymers, and room for improvement in the molecular weight of the manufactured olefin polymers.

[0008] An object of the present invention is to provide a transition metal compound, a catalyst for olefin polymerization, and a method for producing an olefin polymer, which can efficiently produce an olefin polymer represented by an ethylene polymer having a high molecular weight into which many long-chain branches are introduced with high catalytic activity. [Means for Solving the Problems]

[0009] The present inventors conducted intensive research to solve the above problems, and found that a bridged (2-indenyl)(1-indenyl) type compound having a specific substituent on the 1-indenyl ring can solve the above problems, and thus completed the present invention.

[0010] The gist of the present invention is as follows. <1> A transition metal compound [A] represented by the following general formula [1].

[0011] Chemical formula (In general formula [1], M is a group 4 transition metal atom of the periodic table, n is an integer of 1 to 4 selected such that the transition metal compound [A] is electrically neutral, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating via a lone electron pair; the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group or a conjugated diene-derived group; when n is 2 or more, the plurality of groups represented by X may be the same or different from each other, and may be bonded to each other to form a ring, Q is a group 14 atom of the periodic table, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 13 and R14 Each of these is independently a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. R 9 , R 10 , R 11 , R 12 Each of these is independently a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. R 1 ~R 6 Adjacent substituents may bond to each other to form a ring which may also have substituents. R 10 and R 11 These may be bonded to each other to form a ring which may have substituents. R 13 and R 14 These elements may bond to each other to form a ring containing Q, and this ring may have substituents.

[0012] <2> In the above general formula [1], M is a zirconium atom or a hafnium atom, X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an oxygen-containing group. Q is a carbon atom or a silicon atom, R 1 ~R 8 and R 13 ~R 14 However, each is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms, or a sulfur-containing group having 1 to 20 carbon atoms. R 9 ~R 12 However, each of these is independently a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms, or a sulfur-containing group having 1 to 20 carbon atoms, as described above. <1> A transition metal compound [A].

[0013] <3> In the above general formula [1], Q is a silicon atom, R 1 ~R 8 and R 13 ~R 14 However, each is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms. R 9 ~R 12 However, each of them independently is a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms, as described above. <2> A transition metal compound [A].

[0014] <4> In the above general formula [1], R 1 and R 6 However, the aforementioned hydrogen atom <3> A transition metal compound [A].

[0015] <5> In the above general formula [1], R 2 ~R 5 and R 8 However, the aforementioned hydrogen atom <4> A transition metal compound [A].

[0016] <6> In the above general formula [1], R 9 ~R 12 However, each is independently a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, as described above. <5> A transition metal compound [A].

[0017] <7> In the above general formula [1], R 9 ~R 12 However, each is independently a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. R 10 and R11 The above, which do not bond to each other to form a ring. <5> A transition metal compound [A].

[0018] <8> In the above general formula [1], R 9 ~R 12 However, each is independently a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. R 10 and R 11 However, the rings which may be bonded to each other and have substituents, <5> A transition metal compound [A].

[0019] <9> The aforementioned <1> ~ <8> A catalyst for olefin polymerization containing one of the following transition metal compounds [A].

[0020] <10> Furthermore, [B][B-1] organometallic compounds, [B-2] Organoaluminum oxy compounds, and [B-3] The above includes at least one compound selected from the group consisting of compounds that react with transition metal compounds [A] to form ion pairs. <9> A catalyst for olefin polymerization.

[0021] <11> The aforementioned <9> or <10> A method for producing an olefin polymer, comprising the step of polymerizing an olefin in the presence of an olefin polymerization catalyst.

[0022] <12> The step of polymerizing the olefin is a step of homopolymerizing ethylene or a step of copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms. <11> A method for producing olefin polymers. [Effects of the Invention]

[0023] According to the transition metal compound, olefin polymerization catalyst, and method for producing olefin polymers of the present invention, high molecular weight ethylene polymers with many long-chain branches can be produced with high catalytic activity. [Modes for carrying out the invention]

[0024] The following describes the transition metal compounds and the like according to the present invention in more detail. [Transition metal compounds [A]] The transition metal compound [A] (hereinafter sometimes referred to as "component (A)") according to the present invention is represented by the following general formula [1].

[0025] [ka]

[0026] 《M, n, X》 In general formula [1], M is a transition metal atom of group 4 of the periodic table, preferably a zirconium atom or a hafnium atom, and more preferably a zirconium atom. n is an integer between 1 and 4, preferably 1 or 2, selected such that the transition metal compound [A] is electrically neutral.

[0027] X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that can coordinate with a lone pair of electrons, wherein the anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group, or a conjugated diene derivative group. Preferably, X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group.

[0028] If n is 2 or greater, the multiple X elements may be identical or different from each other, and they may be joined together to form a ring. Furthermore, if there are multiple such rings, these rings may be identical or different from each other. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, with chlorine or bromine being preferred.

[0029] Examples of the hydrocarbon group include: Linear or branched alkyl groups such as methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group (butan-2-yl group), tert-butyl group (2-methylpropane-2-yl group), iso-butyl group (2-methylpropyl group), pentan-2-yl group, 2-methylbutyl group, iso-pentyl group (3-methylbutyl group), neopentyl group (2,2-dimethylpropyl group), siamyl group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group (2,3-dimethylbuta-2-yl group), and 4,4-dimethylpentyl group; Vinyl group, allyl group, propenyl group (propa-1-en-1-yl group), iso-propenyl group (propa-1-en-2-yl group), allenyl group (propa-1,2-dien-1-yl group), buta-3-en-1-yl group, clotyl group (buta-2-en-1-yl group), buta-3-en-2-yl group, metharyl group (2-methylallyl group), buta-1,3-dienyl group, pen Linear or branched alkenyl groups or unsaturated double bond-containing groups such as ta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group (3-methylbuta-3-en-1-yl group), 2-methylbuta-3-en-1-yl group, penta-4-en-2-yl group, and prenyl group (3-methylbuta-2-en-1-yl group); Linear or branched alkynyl groups or unsaturated triple bond-containing groups such as ethynyl groups, propa-2-in-1-yl groups, and propargyl groups (propa-1-in-1-yl groups); Aromatic linear or branched alkyl groups and unsaturated double bond-containing groups such as benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-iso-propylbenzyl group), 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, and benzhydryl group (diphenylmethyl group); Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norborneyl group, 1-adamantyl group, 2-adamantyl group, and other cyclic saturated hydrocarbon groups; Aromatic substituents include phenyl group, tolyl group (methylphenyl group), xylyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), juryl group (2,3,5,6-tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, and ferrocenyl group. Among the hydrocarbon groups mentioned above, methyl, iso-butyl, neopentyl, siamyl, benzyl, phenyl, tolyl, xylyl, mesityl, and cumenyl groups are preferred.

[0030] Examples of the halogen-containing groups include fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, and hexachloroantimonate anion. Among the halogen-containing groups, the pentafluorophenyl group is preferred.

[0031] Examples of the silicon-containing groups include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, tris(trimethylsilyl)silyl group, and trimethylsilylmethyl group. Among the silicon-containing groups mentioned above, the trimethylsilylmethyl group is preferred.

[0032] Examples of the oxygen-containing groups include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec-butoxy group, iso-butoxy group, tert-butoxy group, benzyloxy group, methoxymethoxy group, phenoxy group, 2,6-dimethylphenoxy group, 2,6-di-iso-propylphenoxy group, 2,6-di-tert-butylphenoxy group, 2,4,6-trimethylphenoxy group, 2,4,6-tri-iso-propylphenoxy group, acetoxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetoxy group, perchlorate anion, and periodate anion. Among the oxygen-containing groups, methoxy groups, ethoxy groups, iso-propoxy groups, and tert-butoxy groups are preferred.

[0033] Examples of the aforementioned sulfur-containing groups include mesyl group (methanesulfonyl group), phenylsulfonyl group, tosyl group (p-toluenesulfonyl group), trifuryl group (trifluoromethanesulfonyl group), nonafuryl group (nonafluorobutanesulfonyl group), mesylate group (methanesulfonate group), tosylate group (p-toluenesulfonate group), triflate group (trifluoromethanesulfonate group), and nonaflate group (nonafluorobutanesulfonate group). Among the aforementioned sulfur-containing groups, the triflate group (trifluoromethanesulfonate group) is preferred.

[0034] Examples of the nitrogen-containing groups include amino groups, cyano groups, methylamino groups, dimethylamino groups, ethylamino groups, diethylamino groups, allylamino groups, diallylamino groups, benzylamino groups, dibenzylamino groups, pyrrolidinyl groups, piperidinyl groups, morpholyl groups, pyrrolyl groups, and bistrifurylimide groups. Among the nitrogen-containing groups, dimethylamino group, diethylamino group, pyrrolidinyl group, pyrrolyl group, and bistrifurylimide group are preferred.

[0035] Examples of the phosphorus-containing group include the hexafluorophosphate anion. Examples of the boron-containing groups include tetrafluoroborate anion, tetrakis(pentafluorophenyl)borate anion, (methyl)(tris(pentafluorophenyl))borate anion, (benzyl)(tris(pentafluorophenyl))borate anion, tetrakis((3,5-bistrifluoromethyl)phenyl)borate anion, and groups represented by BR4 (where R independently represents a hydrogen atom, an alkyl group, an optionally substituted aryl group, or a halogen atom, etc.).

[0036] Examples of the aforementioned aluminum-containing group are:

[0037] [ka] (M represents M in the general formula [1] above.) Examples of groups that can form a compound include AlR4 (where R is independently a hydrogen atom, an alkyl group, an optionally substituted aryl group, or a halogen atom, etc.).

[0038] Examples of the aforementioned conjugated diene derivative groups include metallocyclopentene groups such as 1,3-butadienyl group, isoprenyl group (2-methyl-1,3-butadienyl group), piperilenyl group (1,3-pentadienyl group), 2,4-hexadienyl group, 1,4-diphenyl-1,3-pentadienyl group, and cyclopentadienyl group.

[0039] Examples of neutral ligands that can coordinate with a lone pair of electrons include ethers such as diethyl ether, tetrahydrofuran, dioxane, and 1,2-dimethoxyethane; amines such as triethylamine and diethylamine; heterocyclic compounds such as pyridine, picoline, lutidine, oxazoline, oxazole, thiazole, imidazole, and thiophene; and organophosphorus compounds such as triphenylphosphine, tricyclohexylphosphine, and tri-tert-butylphosphine.

[0040] 《Q》 In the general formula [1] above, Q is an atom of Group 14 of the periodic table, such as a carbon atom, a silicon atom, a germanium atom, or a tin atom, preferably a carbon atom or a silicon atom, and more preferably a silicon atom.

[0041] 《R 1 ~R 14 》 In the above general formula [1], R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 13 and R 14 Each of these is independently a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group, and R 9 , R 10 , R 11 , R 12 R is a substituent similar to the above, other than a hydrogen atom. 9 ~R 12 By using a transition metal compound [A] in which the substituent is anything other than a hydrogen atom, the catalytic activity of the catalyst for olefin polymerization is significantly improved. In addition, the molecular weight of the ethylene polymer produced is also improved. R 1 ~R 14Examples of hydrocarbon groups having 1 to 40 carbon atoms include hydrocarbon groups having 1 to 20 carbon atoms, and more specifically, specific examples of the hydrocarbon groups listed as examples of X above can be cited.

[0042] The C1-C40 hydrocarbon group is preferably a C1-C20 hydrocarbon group (excluding aromatic hydrocarbon groups) or a C6-C40 aromatic hydrocarbon group. The C1-C20 hydrocarbon group is preferably an aliphatic or alicyclic hydrocarbon group. The C1-C20 hydrocarbon group also includes substituents having an aromatic structure, such as arylalkyl groups.

[0043] Examples of the hydrocarbon group having 1 to 40 carbon atoms are: Methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decanyl group, 1-undecanyl group, 1-dodecanyl group, 1-eicosanyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl group, neopentyl group, tert-pentyl group (1,1-dimethylpropyl group), siamyl group, pentan-3-yl group, 2-methylpentyl group, 3-methylpentyl group, iso-hexyl group, 1,1-dimethylbutyl group (2-methylpentan-2-yl group), 3-methylpentane Linear or branched alkyl groups having 1 to 40 carbon atoms, such as -2-yl group, 4-methylpentan-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group, 3-methylpentan-3-yl group, 3,3-dimethylbuta-2-yl group, hexane-3-yl group, 2-methylpentan-3-yl group, heptane-4-yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,3,3-trimethylbutan-2-yl group, and 2,4,4-trimethylpentan-2-yl group; Vinyl group, allyl group, propenyl group, iso-propenyl group, allenyl group, buta-3-en-1-yl group, clotyl group, buta-3-en-2-yl group, methallyl group, buta-1,3-dienyl group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group, 2-methylbuta-3-en-1-yl group, penta-4-en-2-yl group, prenyl group, 2-methylbuta-2-en-1- Iyl group, penta-3-en-2-yl group, 2-methyl-buta-3-en-2-yl group, penta-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta-1,4-dien-3-yl group, iso-prenyl group (2-methyl-buta-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hexa-5-en-1-yl group, hexa-4-en-1-yl group, hexa-3-en- 1-yl group, hexa-2-en-1-yl group, 4-methyl-penta-4-en-1-yl group, 3-methyl-penta-4-en-1-yl group, 2-methyl-penta-4-en-1-yl group, hexa-5-en-2-yl group, 4-methyl-penta-3-en-1-yl group, 3-methyl-penta-3-en-1-yl group, 2,3-dimethyl-buta-2-en-1-yl group, 2-methylpenta-4-en-2-yl group, 3-ethylpenta-1-en-3 -yl group, hexa-3,5-dien-1-yl group, hexa-2,4-dien-1-yl group, 4-methylpenta-1,3-dien-1-yl group, 2,3-dimethylbuta-1,3-dien-1-yl group, hexa-1,3,5-trien-1-yl group, 2-(cyclopentadienyl)propan-2-yl group, 2-(cyclopentadienyl)ethyl group, etc., linear or branched alkenyl groups or unsaturated double bond-containing groups with 2 to 40 carbon atoms; Ethynyl group, propa-2-in-1-yl group, propargyl group, buta-1-in-1-yl group, buta-2-in-1-yl group, buta-3-in-1-yl group, penta-1-in-1-yl group, penta-2-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1-yl group, 3-methylbuta-1-in-1-yl group, penta-3-in-2-yl group, 2-methylbuta-3-yl Linear or branched alkynyl groups or unsaturated triple bond-containing groups with 2 to 40 carbon atoms, such as 1-yl group, penta-4-in-2-yl group, hexa-1-in-1-yl group, 3,3-dimethylbuta-1-in-1-yl group, 2-methylpenta-3-in-2-yl group, 2,2-dimethylbuta-3-in-1-yl group, hexa-4-in-1-yl group, and hexa-5-in-1-yl group; Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cumyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group, cumyl group (2-phenylpropan-2-yl group), 2-(4-methylphenyl)propan-2-yl group, 2-(3,5-dimethylphenyl)propan-2-yl group, 2-(4-tert-butylphenyl)propan-2-yl group, 2-(3,5-di-tert-butylphenyl)propan-2-yl group, 3-phenylpentan-3-yl group, 4-phenylhepta-1, 6-dien-4-yl group, 1,2,3-triphenylpropane-2-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-buta-3-en-1-yl group, 1,1,2-triphenylethyl group, trityl group (triphenylmethyl group), tri-(4-methylphenyl)methyl group, 2-phenylethyl group, styryl group (2-phenylvinyl group), 2-(2-methylphenyl)ethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-iso-propylphenyl)ethyl group, 2-(4-tert-butylphenyl)ethyl group, 2-(3,5-di-tert-butylphenyl)ethyl group, 2-methyl-1-phenylpropane-2-yl group, 3-phenylpropyl group, cinnamyl group (3-phenylallyl group), neophyll group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutan-2-yl group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propane-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(tetrahydro-1-indacenyl)propane-2-yl group, (tetrahydro-1-indacenyl) Aromatic linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, such as diphenylmethyl group, 2-(tetrahydro-1-indacenyl)ethyl group, 2-(1-benzoindenyl)propan-2-yl group, (1-benzoindenyl)diphenylmethyl group, 2-(1-benzoindenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, 2-(1-azlenyl)propan-2-yl group, (1-azlenyl)diphenylmethyl group, and 2-(1-azlenyl)ethyl group; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl Syl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, cyclooctatrienyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl- tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, 7-methylbicyclo[2.2.1]heptan-7-yl group, bicyclo[2.2.2]octane-1-yl group, bicyclo[2.2.2]octane-2-yl group, 1-adamantyl group, 2-adamantyl group, 1-(2-methyladamantyl), 1-(3-methyladamantyl), 1-(4-methyladamantyl), 1 -(2-phenyladamantyl), 1-(3-phenyladamantyl), 1-(4-phenyladamantyl), 1-(3,5-dimethyladamantyl), 1-(3,5,7-trimethyladamantyl), 1-(3,5,7-triphenyladamantyl), pentarenyl group, indenyl group, fluorenyl group, indacenyl group, tetrahydroindacenyl group, benzoindenyl group, azurenyl group, and other cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms; Examples include aromatic substituents with 6 to 40 carbon atoms, such as phenyl, tolyl, xylyl, mesityl, cumenyl, juryl, 2,6-di-iso-propylphenyl, 2,4,6-tri-iso-propylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, allylphenyl, (buta-3-en-1-yl)phenyl, (buta-2-en-1-yl)phenyl, methallylphenyl, prenylphenyl, 4-adamantylphenyl, 3,5-diadamantylphenyl, naphthyl, biphenyl, terphenyl, binaphthyl, acenaphthalenyl, phenanthryl, anthracenyl, pyrenyl, and ferrocenyl groups.

[0044] Among the linear or branched alkyl groups having 1 to 40 carbon atoms, the following are particularly important: methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, pentan-3-yl group, iso-hexyl group, 1,1-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group, 3-methylpentan-3-yl group, heptane-4 -yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,4,4-trimethylpentan-2-yl group, etc. are preferred, and methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, iso-propyl group, tert-butyl group, neopentyl group, 2,4-dimethylpentan-2-yl group, 2,4,4-trimethylpentan-2-yl group are more preferred.

[0045] Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, vinyl groups, allyl groups, buta-3-en-1-yl groups, clotyl groups, methallyl groups, penta-4-en-1-yl groups, prenyl groups, penta-1,4-dien-3-yl groups, hexa-5-en-1-yl groups, 2-methylpenta-4-en-2-yl groups, 2-(cyclopentadienyl)propane-2-yl groups, and 2-(cyclopentadienyl)ethyl groups are preferred, with vinyl groups, allyl groups, buta-3-en-1-yl groups, penta-4-en-1-yl groups, prenyl groups, and hexa-5-en-1-yl groups being more preferred.

[0046] Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, ethynyl group, propa-2-in-1-yl group, propargyl group, buta-2-in-1-yl group, buta-3-in-1-yl group, penta-3-in-1-yl group, penta-4-in-1-yl group, 3-methyl-buta-1-in-1-yl group, 3,3-dimethyl-buta-1-in-1-yl group, hexa-4-in-1-yl group, hexa-5-in-1-yl group, and more preferably propa-2-in-1-yl group, propargyl group, buta-2-in-1-yl group, and buta-3-in-1-yl group.

[0047] Among the aromatic linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, there are benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-iso-propylphenyl)ethyl group, 2-(4-t The following are preferred: ert-butylphenyl)ethyl group, 2-(3,5-di-tert-butylphenyl)ethyl group, styryl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group, neophyll group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, and more preferably, benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 3-phenylpropyl group, and cinnamyl group.

[0048] Among the aforementioned cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzyl The following are preferred: a cycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, pentarenyl group, indenyl group, fluorenyl group, etc., and more preferably cyclopentyl group, cyclopentenyl group, 1-methylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, and 1-adamantyl group.

[0049] Among the aromatic substituents having 6 to 40 carbon atoms, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, prenylphenyl group, 4-adamanthylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, phenanthryl group, anthracenyl group, and ferrocenyl group are preferred, and phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamanthylphenyl group, naphthyl group, biphenyl group, phenanthryl group, and anthracenyl group are more preferred.

[0050] Examples of the halogen-containing groups include fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, 3,3,3-trifluoropropyl group, nonafluorobutyl group, 4,4,4-trifluorobutyl group, dodecafluorohexyl group, 6,6,6-trifluorohexyl group, chlorophenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, bistrifluoromethoxyphenyl group, trifluoromethylthiophenyl group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluorobiphenyl group, Examples include trifluorobiphenyl group, tetrafluorobiphenyl group, pentafluorobiphenyl group, di-tert-butyl-fluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxybiphenyl group, bistrifluoromethoxybiphenyl group, trifluoromethyldimethylsilyl group, trifluoromethoxy group, pentafluoroethoxy group, fluorophenoxy group, difluorophenoxy group, trifluorophenoxy group, pentafluorophenoxy group, di-tert-butyl-fluorophenoxy group, trifluoromethylphenoxy group, bistrifluoromethylphenoxy group, trifluoromethoxyphenoxy group, bistrifluoromethoxyphenoxy group, difluoromethylenedioxyphenyl group, bistrifluoromethylphenyliminomethyl group, trifluoromethylthio group, and the like.

[0051] Among the halogen-containing groups, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 4,4,4-trifluorobutyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, pentafluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxy group, pentafluorophenoxy group, bistrifluoromethylphenoxy group, bistrifluoromethylphenoxy group, difluoromethylenedioxyphenyl group, and trifluoromethylthio group are preferred, and trifluoromethyl group, fluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, pentafluorobiphenyl group, trifluoromethoxy group, and pentafluorophenoxy group are more preferred.

[0052] Examples of the silicon-containing groups include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, tris(trimethylsilyl)silyl group, cyclopentadienyldimethylsilyl group, di-n-butyl(cyclopentadienyl)silyl group, cyclopentadienyldiphenylsilyl group, indenyldimethylsilyl group, and di-n-butyl(indenyl Examples include silyl groups, indenyldiphenylsilyl groups, fluorenyldimethylsilyl groups, di-n-butyl(fluorenyl)silyl groups, fluorenyldiphenylsilyl groups, 4-trimethylsilylphenyl groups, 4-triethylsilylphenyl groups, 4-tri-iso-propylsilylphenyl groups, 4-tert-butyldiphenylsilylphenyl groups, 4-triphenylsilylphenyl groups, 4-tris(trimethylsilyl)silylphenyl groups, and 3,5-bis(trimethylsilyl)phenyl groups.

[0053] Among the silicon-containing groups mentioned above, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group, cyclopentadienyldiphenylsilyl group, indenyldimethylsilyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-triphenylsilylphenyl group, and 3,5-bis(trimethylsilyl)phenyl group are preferred, and trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, and 3,5-bis(trimethylsilyl)phenyl group are more preferred.

[0054] Examples of the oxygen-containing groups include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, allyloxy group, n-butoxy group, sec-butoxy group, iso-butoxy group, tert-butoxy group, methallyloxy group, prenyloxy group, benzyloxy group, methoxymethoxy group, methoxyethoxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, iso-propoxyphenoxy group, allyloxyphenoxy group, biphenyloxy group, binaphthyloxy group, methoxymethyl group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, allyloxyethyl group, benzyloxyethyl group, phenoxyethyl group, methoxypropyl group, and Examples include lyloxypropyl group, benzyloxypropyl group, phenoxypropyl group, methoxyvinyl group, allyloxyvinyl group, benzyloxyvinyl group, phenoxyvinyl group, methoxyallyl group, allyloxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, di-iso-propoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, tetrahydrofuryl group, pyranyl group, tetrahydropyranyl group, furyl group, benzofuryl group, and dibenzofuryl group.

[0055] Among the oxygen-containing groups, alkoxy groups having 1 to 20 carbon atoms (preferably 1 to 10) are preferred, specifically methoxy group, ethoxy group, iso-propoxy group, allyloxy group, n-butoxy group, tert-butoxy group, prenyloxy group, benzyloxy group, phenoxy group, naphthoxy group, toluyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, methoxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, dioxolanil group, tetramethyldioxolanil group, dioxanil group, dimethyldioxanil group, methoxyphenyl group, i so-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, tetrahydropyranyl group, furfuryl group, benzofuryl group, dibenzofuryl group, etc. are preferred, and methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group, phenoxy group, dimethoxymethyl group, dioxolanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, benzofuryl group, dibenzofuryl group, etc. are more preferred.

[0056] Examples of the nitrogen-containing groups include amino groups, dimethylamino groups, diethylamino groups, allylamino groups, diallylamino groups, didecylamino groups, benzylamino groups, dibenzylamino groups, pyrrolidinyl groups, piperidinyl groups, molyphoyl groups, azepinyl groups, dimethylaminomethyl groups, dibenzylaminomethyl groups, pyrrolidinylmethyl groups, dimethylaminoethyl groups, benzylaminomethyl groups, benzylaminoethyl groups, pyrrolidinylethyl groups, dimethylaminovinyl groups, benzylaminovinyl groups, pyrrolidinylvinyl groups, dimethylaminopropyl groups, benzylaminopropyl groups, pyrrolidinylpropyl groups, dimethylaminoallyl groups, benzylaminoallyl groups, pyrrolidinylallyl groups, aminophenyl groups, dimethylaminophenyl groups, 3,5-dimethyl-4-dimethylaminophenyl groups. Examples include 3,5-di-iso-propyl-4-dimethylaminophenyl group, jurolidinyl group, tetramethyljurolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolyl group, phenylpyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, and benzoxazolyl group.

[0057] Among the nitrogen-containing groups, amino groups having 1 to 20 carbon atoms (preferably 1 to 10) are preferred, specifically amino groups, dimethylamino groups, diethylamino groups, allylamino groups, benzylamino groups, dibenzylamino groups, pyrrolidinyl groups, piperidinyl groups, morpholyl groups, dimethylaminomethyl groups, benzylaminomethyl groups, pyrrolidinylmethyl groups, dimethylaminoethyl groups, pyrrolidinylethyl groups, dimethylaminopropyl groups, pyrrolidinylpropyl groups, dimethylaminoallyl groups, pyrrolidinylallyl groups, aminophenyl groups, dimethylaminophenyl groups, 3,5-dimethyl-4-dimethylaminophenyl groups, 3,5-di-iso-propyl-4-dimethylaminophenyl groups, jurolidinyl groups, tetramethyljurolidinyl groups, pyrrolidinylphenyl groups, pyrrolylphenyl groups, and carbazolylphenyl groups. The following are preferred groups: di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group, etc. More preferred are amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, jurolidinyl group, tetramethyljurolidinyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group, and imidazolyl group.

[0058] Examples of the sulfur-containing groups include methylthio group, ethylthio group, benzylthio group, phenylthio group, naphthylthio group, methylthiomethyl group, benzylthiomethyl group, phenylthiomethyl group, naphthylthiomethyl group, methylthioethyl group, benzylthioethyl group, phenylthioethyl group, naphthylthioethyl group, methylthiovinyl group, benzylthiovinyl group, phenylthiovinyl group, naphthylthiovinyl group, methylthiopropyl group, benzylthiopropyl group, phenylthiopropyl group, naphthylthiopropyl group, methylthioallyl group, benzylthioallyl group, and phenyl Examples include thioallyl group, naphthylthioallyl group, mercaptophenyl group, methylthiophenyl group, thienylphenyl group, methylthienylphenyl group, benzothienylphenyl group, dibenzothienylphenyl group, benzodithienylphenyl group, thienyl group, tetrahydrothienyl group, methylthienyl group, thienofuryl group, thienothienyl group, benzothienyl group, dibenzothienyl group, thienobenzofuryl group, benzodithienyl group, dithiolanyl group, dithianyl group, oxathiolanyl group, oxathianyl group, thiazolyl group, benzothiazolyl group, and thiazolidinyl group.

[0059] Among the sulfur-containing groups mentioned above, thienyl group, methylthienyl group, thienofuryl group, thienothienyl group, benzothienyl group, dibenzothienyl group, thienobenofuryl group, benzodithienyl group, thiazolyl group, and benzothiazolyl group are preferred.

[0060] R 1 ~R 6 Among adjacent substituents (e.g., R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , and R 5 and R 6These rings may bond to each other to form a ring which may have substituents. In this case, the ring formed is preferably a 5-8 membered ring consisting of saturated hydrocarbons (excluding the hydrocarbon of the indenyl ring portion) or unsaturated hydrocarbons which may have substituents and fuse with the indenyl ring portion. If there are multiple rings, they may be the same or different from each other. The present invention is not particularly limited as long as it achieves its effects, but the ring is more preferably a 5 or 6 membered ring. In this case, the structure formed by combining the ring and the indenyl ring portion of the parent nucleus may include, for example, a substituted benzoindenyl ring, a substituted tetrahydroindacene ring, or a substituted cyclopentatetrahydronaphthalene, with substituted benzoindenyl rings and substituted tetrahydroindacene rings being preferred.

[0061] R 10 and R 11 Each substituent does not necessarily have to form a ring; each substituent may bond to each other to form a ring which may have substituents. In this case, the formed ring is preferably a 5-8 membered ring consisting of saturated hydrocarbons (excluding the hydrocarbon of the indenyl ring portion) or unsaturated hydrocarbons which may have substituents and are fused to the indenyl ring portion, and more preferably a 5 or 6 membered ring consisting of saturated hydrocarbons. Furthermore, each substituent which may be present in the 5-8 membered ring is preferably independently a saturated hydrocarbon having 1 to 6 carbon atoms. The ring may have 1 or 2 substituents on one of the carbon atoms constituting the ring. In this case, examples of the ring include a dimethylcyclohexene ring, a diethylcyclopentene ring, a dibutylcyclopentene ring, and a tetramethylcyclohexene ring, with the dibutylcyclopentene ring being preferred.

[0062] R 13 and R 14 These may bond to each other to form a ring containing Q. In this case, the formed ring is preferably a saturated or unsaturated ring of 3 to 8 members, which may have substituents. The ring is not particularly limited as long as the effects of the present invention are achieved, but the ring is preferably a 4 to 6 member ring, in which case R 13 and R 14Examples of the structure combining the above and Q include substituted cyclobutane rings, substituted cyclopentane rings, substituted fluorene rings, substituted silacyclobutane (siletane) rings, substituted silacyclopentane (silolane) rings, substituted silacyclohexane (silinane) rings, and substituted silafluorene rings, with substituted cyclopentane rings, substituted silacyclobutane rings, and substituted silacyclopentane rings being preferred.

[0063] R 1 ~R 6 and R 8 each independently are preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group; more preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms or a nitrogen-containing group having 1 to 20 carbon atoms; and particularly preferably a hydrogen atom.

[0064] R 7 , R 13 and R 14 each independently are preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group; and more preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms or a nitrogen-containing group having 1 to 20 carbon atoms.

[0065] R 9 ~R 12 each independently are preferably a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group; more preferably a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms or a nitrogen-containing group having 1 to 20 carbon atoms; and particularly preferably a saturated hydrocarbon group having 1 to 20 carbon atoms. Note that for at least one of R 7 , R 9 and R 12 , and particularly for R 7 , the oxygen-containing group, nitrogen-containing group or sulfur-containing group may be a heterocyclic aromatic group described later.

[0066] Preferred embodiment of the transition metal compound [A] A preferred embodiment of the transition metal compound [A] is: In the above general formula [1], M is a zirconium atom or a hafnium atom, X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an oxygen-containing group. Q is a carbon atom or a silicon atom, R 1 ~R 8 and R 13 ~R 14 However, each is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms, or a sulfur-containing group having 1 to 20 carbon atoms. R 9 ~R 12 However, examples include transition metal compounds [A-1] which are hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups having 1 to 20 carbon atoms, oxygen-containing groups having 1 to 20 carbon atoms, nitrogen-containing groups having 1 to 20 carbon atoms, or sulfur-containing groups having 1 to 20 carbon atoms, and a more preferred embodiment is: In the above general formula [1], Q is a silicon atom, R 1 ~R 8 and R 13 ~R 14 However, each is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms. R 9 ~R 12 However, examples include transition metal compounds [A-2] which are hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups having 1 to 20 carbon atoms, oxygen-containing groups having 1 to 20 carbon atoms, or nitrogen-containing groups having 1 to 20 carbon atoms. A more preferred embodiment of the transition metal compound [A-2] is one in which R in the general formula [1] 1 ~R 6 and R 8 That is a hydrogen atom, R9 ~R 12 However, examples include transition metal compounds [A-3] which are saturated hydrocarbon groups having 1 to 20 carbon atoms.

[0067] In the transition metal compound [A-1], R 7 , R 9 and R 12 One of the options is a heterocyclic aromatic group which may have substituents and whose parent skeleton is a five-membered ring (hereinafter also called a "hetero-five-membered ring") containing at least one atom selected from the group consisting of nitrogen, oxygen, and sulfur. For example, a group represented by the following general formulas [4a] to [4h] is shown below.

[0068] [ka]

[0069] In the above general formulas [4a] to [4h], Ch is an oxygen atom or a sulfur atom, and R d Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different. In addition, the dashed lines in the general formulas [4a] to [4h] indicate the bonding site with the indenyl ring.

[0070] Examples of the hydrocarbon groups having 1 to 20 carbon atoms include the above-mentioned R 1 ~R 14Among the examples of hydrocarbon groups having 1 to 40 carbon atoms, those having 1 to 20 carbon atoms are particularly noteworthy, and preferably include methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, allyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctenyl group, norbornyl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, and 3-phenyl Examples of groups include propyl group, cinnamyl group, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, phenanthryl group, anthracenyl group, and ferrocenyl group. More preferably, examples include methyl group, ethyl group, 1-propyl group, 1-butyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, allyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, biphenyl group, and terphenyl group.

[0071] R d Each is independent of the adjacent R dThey may bond with each other and fuse to form saturated or unsaturated hydrocarbon groups that constitute a 5- to 8-membered ring together with the atoms of the heterogeneous 5-membered ring, which may have substituents. The 5- to 8-membered ring is not particularly limited as long as it achieves the effects of the present invention, but is preferably a 5 or 6-membered ring. In this case, examples of structures formed by combining this ring with the heterogeneous 5-membered ring of the parent nucleus include a benzofuran ring, a benzothiophene ring, an indole ring, a carbazole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, and a benzopyrazole ring.

[0072] Among the heterocyclic aromatic groups represented by the general formulas [4a] to [4h], the heterocyclic aromatic group represented by the general formula [4a] is preferred. Among the heterocyclic aromatic groups represented by the general formula [4a], the 2-furyl group, the 5-methyl-2-furyl group, the 2-thienyl group, and the 5-methyl-2-thienyl group are preferred.

[0073] Examples of transition metal compounds [A] Specific examples of the transition metal compound [A] are shown below, but this does not particularly limit the scope of the present invention.

[0074] For convenience, the ligand structure of the transition metal compound [A] excluding the MXn (metal portion) portion is referred to as the 2-indenyl ring portion, the 1-indenyl ring portion, and the 2-indenyl ring portion R 1 and R 6 Substituents and 1-indenyl ring portion R 8 Substituents, 2-indenyl ring portion R 2 and R 5 Substituents, 2-indenyl ring portion R 3 and R 4 Substituents, 1-indenyl ring portion R 9 , R 10 , R 11 and R 12 , 1-indenyl ring portion R 7 The structure is divided into eight parts: substituents and bridging regions. The abbreviation for the 2-indenyl ring portion is α, the abbreviation for the 1-indenyl ring portion is β, and the abbreviation for the 2-indenyl ring portion is R. 1 and R6 Substituents and 1-indenyl ring portion R 8 The substituent is abbreviated as γ, and the 2-indenyl ring portion is R. 2 and R 5 The substituent is abbreviated as δ, and the 2-indenyl ring portion is R. 3 and R 4 The substituent is abbreviated as ε, and the 1-indenyl ring portion is R. 9 , R 10 , R 11 and R 12 The abbreviation for the substituent is ζ, and the 1-indenyl ring portion is R. 7 The abbreviation for substituents is η, and the abbreviation for the structure of the bridging portion is θ. The abbreviations for each substituent are shown in [Table 1] to [Table 8].

[0075] [Table 1]

[0076] [Table 2] Note that the dashed lines in [Table 1] to [Table 2] indicate the connection points with the bridged portion. R in [Table 2] β is, R 10 and R 11 The R β Each substituent is independently a saturated hydrocarbon having 1 to 6 carbon atoms.

[0077] [Table 3] R in [Table 3] above 1 , R 6 and R 8 The substituents may be identical or different from one another in their combination.

[0078] [Table 4] R in [Table 4] above 2 and R 5 The substituents may be identical or different from one another in their combination.

[0079] [Table 5] R in [Table 5] above 3 and R 4 The substituents may be identical or different from one another in their combination.

[0080] [Table 6] R in [Table 6] above 9 , R 10 , R 11 and R 12 The substituents may be identical or different from one another in their combination.

[0081] [Table 7]

[0082] [Table 8]

[0083] Specific examples of the metallic part MXn include TiF2, TiCl2, TiBr2, TiI2, Ti(Me)2, Ti(Bn)2, Ti(Allyl)2, Ti(CH2-tBu)2, Ti(1,3-butadienyl), Ti(1,3-pentadienyl), Ti(2,4-hexadienyl), Ti(1,4-diphenyl-1,3-pentadienyl), and Ti(CH2-S i(Me)3)2, Ti(OMe)2, Ti(OiPr)2, Ti(NMe2)2, Ti(OMs)2, Ti(OTs)2, Ti(OTf)2, ZrF2, ZrCl2, ZrBr2, ZrI2, Zr(Me)2, Zr(Bn)2, Zr(Allyl)2, Zr(CH2-tBu)2, Zr(1,3-butadienyl), Zr(1,3-pentadienyl), Zr(2, 4-Hexadienyl), Zr(1,4-diphenyl-1,3-pentadienyl), Zr(CH2-Si(Me)3)2, Zr(OMe)2, Zr(OiPr)2, Zr(NMe2)2, Zr(OMs)2, Zr(OTs)2, Zr(OTf)2, HfF2, HfCl2, HfBr2, HfI2, Hf(Me)2, Hf(Bn)2, Hf(Allyl)2, Hf(C Examples include H2-tBu)2, Hf(1,3-butadienyl), Hf(1,3-pentadienyl), Hf(2,4-hexadienyl), Hf(1,4-diphenyl-1,3-pentadienyl), Hf(CH2-Si(Me)3)2, Hf(OMe)2, Hf(OiPr)2, Hf(NMe2)2, Hf(OMs)2, Hf(OTs)2, and Hf(OTf)2. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si(Me)3 is a trimethylsilyl group, OME is a methoxy group, OiPr is an iso-propoxy group, NMe2 is a dimethylamino group, OMs is a methanesulfonate group, OTs is a p-toluenesulfonate group, and OTf is a trifluoromethanesulfonate group.

[0084] According to the above notation, the 2-indenyl ring portion is α-1 in [Table 1], and the 1-indenyl ring portion is β-3(R in [Table 2]). β (Substitution is a methyl group), 2-indenyl ring portion R 1 and R 6 Substituents and 1-indenyl ring portion R 8All substituents are the γ-1,2-indenyl ring portion R in [Table 3]. 2 and R 5 All substituents are the δ-1,2-indenyl ring moiety R in [Table 4] 3 and R 4 All substituents are the ε-1,1-indenyl ring moiety R in [Table 5] 7 The substituent is η-30, 1-indenyl ring portion R in [Table 7] 9 The substituent is the ζ-8, 1-indenyl ring portion R in [Table 6] 12 When the substituent is composed of the combination of ζ-3 in [Table 6] and the bridging portion is composed of the combination of θ-20 in [Table 8], and the metal portion MXn is ZrCl2, the compound represented by the following formula [5] is an example.

[0085] [ka]

[0086] Furthermore, the 2-indenyl ring portion is α-1 in [Table 1], the 1-indenyl ring portion is β-1 in [Table 2], and the 2-indenyl ring portion is R 1 and R 6 Substituents and 1-indenyl ring portion R 8 All substituents are the γ-1,2-indenyl ring portion R in [Table 3]. 2 and R 5 All substituents are the δ-2,2-indenyl ring moiety R in [Table 4] 3 and R 4 All substituents are the ε-1,1-indenyl ring moiety R in [Table 5] 9 , R 10 , R 11 and R 12 All substituents are the ζ-2,1-indenyl ring moiety R in [Table 6] 7 When the substituent is composed of η-2 in [Table 7] and the bridging portion is composed of θ-20 in [Table 8], and the metal portion MXn is ZrCl2, the compound represented by the following formula [6] is an example.

[0087] [ka]

[0088] Furthermore, the 2-indenyl ring portion is α-3 in [Table 1], the 1-indenyl ring portion is β-1 in [Table 2], and the 2-indenyl ring portion is R 1 and R 6 All substituents are the γ-2,2-indenyl ring portion R in [Table 3]. 2 and R 5 All substituents are the δ-1,1-indenyl ring moiety R in [Table 4] 8 The substituent is the γ-1,1-indenyl ring portion R in [Table 3] 9 The substituent is the ζ-10, 1-indenyl ring portion R in [Table 6] 10 and R 12 All substituents are the ζ-1,1-indenyl ring moiety R in [Table 6] 11 The substituent is the ζ-8, 1-indenyl ring portion R in [Table 6] 7 When the substituent is composed of η-12 in [Table 7] and the bridging portion is composed of θ-31 in [Table 8], and the MXn in the metal portion is HfMe2, the compound represented by the following formula [7] is an example.

[0089] [ka]

[0090] Furthermore, the 2-indenyl ring portion is α-1 in [Table 1], the 1-indenyl ring portion is β-1 in [Table 2], and the 2-indenyl ring portion is R 1 and R 6 All substituents are the γ-1,2-indenyl ring portion R in [Table 3]. 2 The substituent is the δ-7,2-indenyl ring portion R in [Table 4] 3 , R 4 All substituents are the ε-1,2-indenyl ring moiety R in [Table 5] 5 The substituent is the δ-2,1-indenyl ring portion R in [Table 4] 8 The substituent is the γ-9,1-indenyl ring portion R in [Table 3] 9 and R 12 All substituents are the ζ-1,1-indenyl ring moiety R in [Table 6] 10 and R 11All substituents are the ζ-4, 1-indenyl ring portion R in [Table 6] 7 When the substituent is composed of the combination of η-1 in [Table 7] and the bridging portion is composed of the combination of θ-4 in [Table 8], and the MXn of the metal portion is Ti(1,3-pentadienyl), the compound represented by the following formula [8] is an example.

[0091] [ka]

[0092] Furthermore, the transition metal compound [A] has two planes (front and back) for the indenyl ring portion that bonds to the central metal, flanking the bridged portion. Therefore, when there is no plane of symmetry for the 2-indenyl ring portion, there are two structural isomers, as shown by the following general formulas [9a] or [9b], as an example.

[0093] [ka]

[0094] Similarly, substituent R in the crosslinked portion 13 and R 14 Even when they are not identical, there are two structural isomers, for example, represented by the following general formulas [10a] or [10b].

[0095] [ka]

[0096] The purification, separation, or selective production of these structural isomer mixtures is possible by known methods, and the production method is not particularly limited. Known production methods include those listed above as methods for producing the transition metal compound [A], as well as methods disclosed in Japanese Patent Publication No. 10-109996, "Organometallics 1999, 18, 5347," "Organometallics 2012, 31, 4340," and Japanese Patent Publication No. 2011-502192.

[0097] Within the range of the transition metal compound [A], one transition metal compound may be used alone, two or more may be used in combination, a mixture of structural isomers may be used, one structural isomer may be used alone, or a mixture of two or more structural isomers may be used. As described above, according to the present invention, an ethylene polymer with many long-chain branches can be produced with high catalytic activity by using only the transition metal compound [A] as the transition metal compound constituting the catalyst for olefin polymerization. However, within a range where this effect is not impaired, one or more transition metal compounds other than the transition metal compound [A] may be used in combination. In this case, the transition metal compound [A] may be any of the above embodiments.

[0098] Method for producing transition metal compounds [A] The transition metal compound [A] can be produced using conventionally known methods, and examples of typical synthesis routes are shown below, but the production method is not particularly limited. Note that in the following [Equations 1] to [Equations 5], R 1 ~R 14 Q, M, X, and n are equivalent to those described in the general formula [1] above.

[0099] The substituted indene compounds used as starting materials can be produced by known methods, and the production method is not particularly limited. Examples of known production methods include, for example, "Organometallics 1994, 13, 954," "Organometallics 2006, 25, 1217," JP 2006-509059, "Bioorg.Med.Chem. 2008, 16, 7399," WO2009 / 080216, "Organometallics 2011, 30, 5744," JP 2011-500800, "Organometallics 2012, 31, 4962," and "Chem.Eur.J." Examples of manufacturing methods disclosed in Japanese Patent Publication No. 2012, 18, 4174, Japanese Patent Publication No. 2012-012307, Japanese Patent Publication No. 2012-121882, Japanese Patent Publication No. 2014-196319, Japanese Patent Publication No. 2014-513735, Japanese Patent Publication No. 2015-063495, Japanese Patent Publication No. 2016-501952, etc.

[0100] Of the aforementioned substituted indene compounds, those that are unsubstituted at the 2-position can be brominated at the 2-position by known methods as described below, and the manufacturing method is not particularly limited.

[0101] [ka]

[0102] In Formula 1, NBS represents N-bromosuccinimide, and PTSA represents p-toluenesulfonic acid or its monohydrate. Indene compounds have five-membered ring partial double bond positional isomers, and mixtures of these isomers may be used. Known manufacturing methods include, for example, those disclosed in Japanese Patent Publication No. 2012-121882 and Japanese Patent Publication No. 2015-063495 mentioned above, as well as those disclosed in Japanese Patent Publication No. 2014-111568 and others.

[0103] The aforementioned 2-position brominated indene compounds and 4-position brominated indene compounds can be used to produce the corresponding coupling products by known methods such as the Suzuki-Miyaura coupling reaction catalyzed with palladium, and the production method is not particularly limited.

[0104] [ka]

[0105] Similarly, indene compounds have positional isomers of the 5-membered ring partial double bond, but a mixture of these isomers may also be used. Furthermore, other boron compounds such as various boronic acid esters or boroxine may be used instead of boronic acid, and the reaction mixture of a halogen compound, a metal reagent, and then a boron compound may be used without isolation and purification. A nickel catalyst or an iron catalyst may also be used instead of a palladium catalyst. Known manufacturing methods include, in addition to those mentioned above, Japanese Patent Application Publication No. 2014-196274.

[0106] Furthermore, instead of the Suzuki-Miyaura coupling reaction with boron compounds, the following methods may be used to produce the coupling product: Negishi coupling with organozinc reagents, the Mizoroki-Heck reaction with alkene compounds, the Hiyama coupling with organosilicon compounds, the Sonogashira-Hagiwara coupling with terminal alkyne compounds, the Migita-Kosugi-Stille coupling with organotin compounds, the Kumada-Tamao-Corriu coupling with organomagnesium compounds, the Buchwald-Hartwig coupling, the Goldberg amination reaction, or the Ullmann ether synthesis reaction. Known production methods, in addition to those mentioned above, include, for example, those described in Japanese Patent Publication No. Hei 8-183814, Japanese Patent Publication No. 2005-529865, and Japanese Patent Publication No. 2006-509046.

[0107] For the production of the coupling product, the aforementioned 2-position unsubstituted indene compound and an aromatic halide may be used, and known methods such as a palladium-catalyzed direct coupling reaction may be employed.

[0108] [ka]

[0109] In the above [Formula 3], Ar represents an aromatic substituent, and a mixture of positional isomers of the indene compound's five-membered ring partial double bond may be used. Known production methods include, for example, Japanese Patent Publication No. 2000-512661 and Japanese Patent Application Publication No. 2014-201519.

[0110] The transition metal compound [A] and precursor compound (ligand) can be produced by known methods using various substituted indene compounds produced by the above-mentioned methods. When Q is a silicon atom, germanium atom, or tin atom, it can be produced by the following methods, and the production method is not particularly limited.

[0111] [ka]

[0112] In the above [Formula 4], in the synthesis of the precursor compound (ligand), the organomagnesium reagent prepared from the 2-brominated indene compound and the organolithium reagent prepared from the substituted 1-indene compound are preferably reacted stepwise with a chloride containing Q, and the order of these reactions is not limited to any particular sequence. After the first reaction with the organometallic reagent, the by-product inorganic compounds may be removed under an inert atmosphere, or the reaction product may be isolated by distillation, crystallization, or washing before use. During the second reaction with the organometallic reagent, it is preferable to add 0.1 to 5.0 equivalents of DMI (1,3-dimethyl-2-imidazolidinone), DMPU (N,N'-dimethylpropylene urea), or HMPA (hexamethyl phosphate triamide) relative to the organometallic reagent, more preferably DMI in an amount of 1.0 equivalent. Note that there are positional isomers of the 5-membered ring partial double bond of the indene compound in the substituted indene compound and the precursor compound (ligand), and a mixture of these isomers may be used.

[0113] Known methods for producing transition metal compounds [A] and precursor compounds (ligands) include, in addition to those mentioned above, Japanese Patent Publication No. 11-315089, Japanese Patent Publication No. 2001-302687, Japanese Patent Publication No. 2001-220404, "Journal of Polymer Science, Japan 2002, 59, 243," Japanese Patent Publication No. 2003-522194, "Macromolecules 2004, 37, 2342," Japanese Patent Publication No. 2007-320935, and Japanese Patent Publication No. 2011-126813.

[0114] If Q is a carbon atom, it can be manufactured by the following methods, and the manufacturing method is not particularly limited.

[0115] [ka]

[0116] In the above [Formula 5], the base is a basic substance capable of generating an indenyl anion, and examples include organometallic compounds such as sodium hydride, n-butyllithium, and Grignard reagents, inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as diethylamine and pyrrolidine, but are not particularly limited. In the presence of a basic substance, a flubene compound can be synthesized from a substituted 1-indene compound and a carbonyl compound by known methods, and a precursor compound (ligand) can be produced by reaction with an organomagnesium reagent prepared from a 2-brominated substituted indene compound. Note that there are positional isomers of the 5-membered ring partial double bond of the indene compound in the substituted indene compound and the precursor compound (ligand), but a mixture of these isomers may be used.

[0117] As known production methods for transition metal compound [A] and precursor compound (ligand), for example, in addition to those described above, "Macromolecules 2003, 36, 9325.", "Organometallics 2004, 23, 5332.", "Eur. J. Inorg. Chem. 2005, 1003.", "Eur. J. Inorg. Chem. 2009, 1759.", and the like can be mentioned.

[0118] [Catalyst for olefin polymerization] The olefin polymerization catalyst of the present invention contains the transition metal compound [A] of the present invention. Typical examples of the olefin polymerization catalyst of the present invention include ethylene polymerization catalysts.

[0119] (Compound [B]) The olefin polymerization catalyst of the present invention preferably further comprises [B-1] an organometallic compound, preferably an organometallic compound represented by the following general formula (B-1a), (B-1b) or (B-1c) (hereinafter also referred to as "component (B-1)"), R a m Al(OR b ) n H p X q ...(B-1a) [In the general formula (B-1a), R a and R b each represent a hydrocarbon group having 1 to 15 carbon atoms, and may be the same or different from each other; X represents a halogen atom; m is a number satisfying 0<m≤3, n is a number satisfying 0≤n<3, p is a number satisfying 0≤p<3, q is a number satisfying 0≤q<3, and m+n+p+q=3.]] M a AlR a ₄...(B-1b) [In the general formula (B-1b), M a represents Li, Na or K, and R a represents a hydrocarbon group having 1 to 15 carbon atoms.]] R a r M b R bs X t …(B-1c) [In general formula (B-1c), R a and R b M represents a hydrocarbon group having 1 to 15 carbon atoms, and these groups may be identical or different from each other. b is selected from Mg, Zn, and Cd, X represents a halogen atom, and r is 0 <r≦2、sは0≦s≦1、tは0≦t≦1であり、かつr+s+t=2である。〕 [B-2]Organoaluminum oxy compounds (hereinafter also referred to as "component (B-2)"), and [B-3] The compound contains at least one compound [B] (hereinafter sometimes referred to as "component (B)") selected from the group consisting of compounds that react with transition metal compounds [A] to form ion pairs (hereinafter also referred to as "component (B)"), which react with transition metal compounds [A] to form ion pairs.

[0120] As the organometallic compound [B-1], any compound disclosed in Japanese Patent Publication No. 11-315109 or EP0874005A by the present applicant can be used without limitation.

[0121] The organometallic compound [B-1] is preferably one represented by the general formula (B-1a), specifically trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, and dimethylaluminum bromide; alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; methylaluminum dichloride; ethylaluminum dichloride Examples include alkylaluminum dihalides such as loride, isopropylaluminum dichloride, and ethylaluminum dibromide; alkylaluminum hydrides such as dimethylaluminum hydride, diethylaluminum hydride, dihydrophenylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diisohexylaluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, di-sec-heptylaluminum hydride, and di-sec-nonylaluminum hydride; and dialkylaluminum alkoxides such as dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide, and diisobutylaluminum ethoxide. These can be used individually or in combination of two or more types.

[0122] As said organoaluminum oxy compound [B-2], aluminoxanes prepared from trialkylaluminum and tricycloalkylaluminum are preferred, and organoaluminum oxy compounds prepared from trimethylaluminum or triisobutylaluminum are particularly preferred. Such organoaluminum oxy compounds may be used alone or in combination of two or more thereof.

[0123] As the compound [B-3] that reacts with the transition metal compound [A] to form an ion pair, there may be mentioned, without limitation, Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP Kohyo 1-501950, JP Kohyo 1-502036, JP Kokai 3-179005, JP Kokai 3-179006, JP Kokai 3-207703, JP Kokai 3-207704, U.S. Patent No. 5321106, and further, heteropoly compounds and isopoly compounds can also be used without limitation.

[0124] In the olefin polymerization catalyst according to the present invention, when the organoaluminum oxy compound [B-2] such as methylaluminoxane is used in combination as a cocatalyst component, the catalyst not only exhibits extremely high catalytic activity for olefins such as ethylene, but also can react with active hydrogen in a solid support to easily prepare a solid support component containing the cocatalyst component. Therefore, it is preferable to use the organoaluminum oxy compound [B-2] as the component (B).

[0125] (Solid carrier [S]) The olefin polymerization catalyst of the present invention preferably contains a solid support [S] (hereinafter sometimes referred to as "support [S]" or "component (S)"). The solid support [S] is an inorganic or organic compound, and is a granular or fine particulate solid. As the inorganic compound, porous oxides, solid aluminoxane compounds, inorganic halides, clays, clay minerals, or ion-exchangeable layered compounds are preferred.

[0126] Specific examples of the porous oxide that can be used include SiO₂, Al₂O₃, MgO, ZrO, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂, etc., or composites or mixtures containing these; further, for example, natural or synthetic zeolites, SiO₂-MgO, SiO₂-Al₂O₃, SiO₂-TiO₂, SiO₂-V₂O₅, SiO₂-Cr₂O₃, SiO₂-TiO₂-MgO, etc. can be used. Among these, porous oxides containing SiO₂ and / or Al₂O₃ as a main component are preferable. The porous oxide may contain a small amount of components such as carbonates, sulfates, nitrates and oxides including Na₂CO₃, K₂CO₃, CaCO₃, MgCO₃, Na₂SO₄, Al₂(SO₄)₃, BaSO₄, KNO₃, Mg(NO₃)₂, Al(NO₃)₃, Na₂O, K₂O, Li₂O, etc. without any adverse effect.

[0127] Although the properties of the porous oxide vary depending on the type and production method thereof, the porous oxide preferably used in the present invention has a particle diameter of 10 to 300 µm, preferably 20 to 200 µm, and a specific surface area of 50 to 1000 m 2 / g, preferably 100 to 700 m 2 / g, and a pore volume of 0.3 to 3.0 cm 3 / g. Such porous oxide is used after calcined at 100 to 1000°C, preferably 150 to 700°C, if necessary.

[0128] The solid aluminoxane compound is selected from at least one of the following: an aluminoxane having a structure represented by the following general formula (S-a) or (S-b), and an aluminoxane having, as a structure, a repeating unit represented by the following general formula (S-c) and a repeating unit represented by the following general formula (S-d).

[0129] Chemical Formula

[0130] In the general formulas (S-a) to (S-c), Re Each of these is independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Specifically, examples of hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, cyclohexyl group, cyclooctyl group, phenyl group, tolyl group, and ethylphenyl group. Methyl group, ethyl group, and isobutyl group are preferred, and methyl group is particularly preferred. Also, R e A portion of it is substituted with halogen atoms such as chlorine and bromine, and the halogen content is R e The amount may be 40% by weight or less based on the standard. In the general formulas (Sc) and (Sd), the straight line on one side that is not connected to an atom indicates a bond with another atom not shown.

[0131] In the general formulas (Sa) and (Sb), r is an integer between 2 and 500, preferably between 6 and 300, and particularly preferably between 10 and 100. In the general formulas (Sc) and (Sd), s and t are each integers of 1 or more. r, s, and t are selected so that the aluminoxane can maintain a substantially solid state under the reaction environment in which it is used.

[0132] Unlike conventionally known carriers for olefin polymerization catalysts, the solid aluminoxane compound does not contain inorganic solid components such as silica or alumina, or organic polymer components such as polyethylene or polystyrene, and is solidified with alkylaluminum compounds as the main component. "Solid" means that the aluminoxane component maintains a substantially solid state under the reaction environment in which it is used. More specifically, this means that the aluminoxane component maintains a substantially solid state when preparing an olefin polymerization catalyst (e.g., an ethylene polymerization catalyst) by contacting the transition metal compound [A] and the aluminoxane component as described later, and when performing polymerization of olefins (e.g., ethylene) using the prepared olefin polymerization catalyst (e.g., suspension polymerization).

[0133] The simplest way to determine whether the aluminoxane component is in a solid state is by visual inspection, but this is often difficult, for example, during polymerization. In such cases, it is possible to determine this from, for example, the properties of the polymer powder obtained after polymerization or the degree of adhesion to the reactor. Conversely, if the properties of the polymer powder are good and there is little adhesion to the reactor, even if some of the aluminoxane component dissolves under the polymerization environment, it does not deviate from the spirit of the present invention. Indicators for determining the properties of the polymer powder include bulk density, particle shape, surface shape, and the degree of presence of amorphous polymers, but polymer bulk density is preferred from the viewpoint of quantitative accuracy. The bulk density is usually in the range of 0.01 to 0.9, preferably 0.05 to 0.6, and more preferably 0.1 to 0.5.

[0134] The dissolution rate of the solid aluminoxane compound in n-hexane held at a temperature of 25°C is typically in the range of 0 to 40 mol%, preferably 0 to 20 mol%, and particularly preferably 0 to 10 mol%.

[0135] The aforementioned dissolution ratio is determined by adding 2 g of a solid aluminoxane compound support to 50 ml of n-hexane maintained at 25°C, stirring for 2 hours, then separating the solution using a G-4 glass filter, and measuring the aluminum concentration in the filtrate. Therefore, the dissolution ratio is determined as the ratio of aluminum atoms present in the filtrate to the amount of aluminum atoms corresponding to 2 g of aluminoxane used.

[0136] As the solid aluminoxane compound, any known solid aluminoxane can be used without limit, and for example, the solid polyaluminoxane composition described in International Publication No. 2014 / 123212 can be used. Known manufacturing methods include, for example, those described in Japanese Patent Publication No. 7-42301, Japanese Patent Publication No. 6-220126, Japanese Patent Publication No. 6-220128, Japanese Patent Publication No. 11-140113, Japanese Patent Publication No. 11-310607, Japanese Patent Publication No. 2000-38410, Japanese Patent Publication No. 2000-95810, and International Publication No. 2010 / 55652.

[0137] The average particle size of the solid aluminoxane compound is generally in the range of 0.01 to 50,000 μm, preferably 1 to 1,000 μm, and particularly preferably 1 to 200 μm. The average particle size of the solid aluminoxane compound is determined by observing the particles with a scanning electron microscope, measuring the particle size of 100 or more particles, and weight averaging them. First, the particle size of each particle is determined by measuring the length of two parallel lines that sandwich the particle image horizontally and vertically, and using the following formula. Particle size = ((horizontal length)) 2 + (vertical length) 2 ) 0.5 Next, the weight-average particle size of the solid aluminoxane compound can be calculated using the particle size obtained above, according to the following formula. Average particle diameter=Σnd 4 / Σnd 3 (n: number of particles, d: particle size)

[0138] The solid aluminoxane compound has a specific surface area of ​​50 to 1000 m². 2 / g, preferably 100-800m 2 The density is / g, and the pore volume is 0.1-2.5 cm³. 3 It is preferable that the value be / g.

[0139] Examples of inorganic halides include MgCl2, MgBr2, MnCl2, and MnBr2. The inorganic halides may be used as is, or they may be ground using a ball mill or vibration mill before use. Alternatively, the inorganic halides can be dissolved in a solvent such as alcohol, and then precipitated into fine particles using a precipitating agent.

[0140] The aforementioned clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystalline structure in which planes formed by ionic bonds are stacked parallel to each other with weak bonding forces, and the ions it contains are exchangeable. Most clay minerals are ion-exchangeable layered compounds. Furthermore, these clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural sources; artificially synthesized materials can also be used.

[0141] Furthermore, examples of clay, clay minerals, or ion-exchangeable layered compounds include ionic crystalline compounds having layered crystalline structures such as hexagonal close-packing type, antimony type, CdCl2 type, and CdI2 type. Furthermore, clays and clay minerals include kaolin, bentonite, kibushi clay, gylome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, lyokdiite group, palygorskite, kaolinite, nacrite, dickite, and halloysite. Examples of ion-exchangeable layered compounds include crystalline acidic salts of polyvalent metals such as α-Zr(HAsO4)2·H2O, α-Zr(HPO4)2, α-Zr(KPO4)2·3H2O, α-Ti(HPO4)2, α-Ti(HAsO4)2·H2O, α-Sn(HPO4)2·H2O, γ-Zr(HPO4)2, γ-Ti(HPO4)2, and γ-Ti(NH4PO4)2·H2O.

[0142] Such clays, clay minerals, or ion-exchangeable layered compounds preferably have a pore volume of 0.1 cc / g or more, and particularly preferably 0.3 to 5 cc / g, as measured by the mercury intrusion method for pores with a radius of 20 Å or more. Here, the pore volume is measured in the range of pore radii from 20 to 30,000 Å by the mercury intrusion method using a mercury porosimeter. When using a support material with a pore volume of less than 0.1 cc / g and a radius of 20 Å or more, it tends to be difficult to obtain high polymerization activity.

[0143] It is also preferable to subject the aforementioned clay and clay minerals to chemical treatment. Chemical treatments can include surface treatments to remove impurities adhering to the surface, and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment. Acid treatment removes surface impurities and increases the surface area by dissolving cations such as Al, Fe, and Mg in the crystalline structure. Alkali treatment destroys the crystalline structure of the clay, leading to a change in its structure. Salt treatment and organic treatment can form ionic complexes, molecular complexes, and organic derivatives, thereby altering the surface area and interlayer distance.

[0144] The aforementioned ion-exchangeable layered compound may be a layered compound in which the interlayers are expanded by utilizing ion exchange properties and exchanging the exchangeable ions between layers with other large, bulky ions. Such bulky ions play a supporting role in the layered structure and are usually called pillars. The introduction of another substance between the layers of a layered compound in this way is called intercalation. Examples of guest compounds for intercalation include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (where R is a hydrocarbon group, etc.), and [Al 13 O4(OH) 24 ] 7+ [Zr4(OH) 14 ] 2+ [Fe3O(OCOCH3)6] +Examples thereof include metal hydroxide ions such as the above. These compounds may be used singly or in combination of two or more kinds. Further, when intercalating these compounds, polymers obtained by hydrolyzing metal alkoxides such as Si(OR)4, Al(OR)3 and Ge(OR)4 (R represents a hydrocarbon group or the like), colloidal inorganic compounds such as SiO2, and the like can be allowed to coexist. Examples of pillars also include oxides formed by intercalating the above metal hydroxide ions between layers and then performing heat dehydration.

[0145] The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as obtained, or may be used after being subjected to treatments such as ball milling and sieving. Alternatively, they may be used after newly adding and adsorbing water, or after being subjected to a heat dehydration treatment. Further, they may be used singly or in combination of two or more kinds. Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, hectorite and synthetic mica.

[0146] Examples of the organic compound that can be used as the carrier [S] include granular or fine-particle solids having a particle diameter in the range of 1 to 300 µm. Specific examples thereof include polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, polymers produced mainly from vinylcyclohexane and styrene, and modified products thereof.

[0147] <Method of Using Each Component and Order of Addition> The olefin polymerization catalyst according to the present invention can be prepared by mixing and bringing component (A), optional component (S), and optional component (B) into contact with each other in an inert hydrocarbon. Regarding the method of bringing each component into contact, focusing on the order of contact, for example: (i) a method of bringing component (B) into contact with component (A), (ii) A method of bringing component (A) into contact with component (S), (iii) A method of bringing component (S) into contact with component (B), and then component (A), (iv) A method of bringing component (A) into contact with component (B), and then component (S), (v) A method of contacting component (S) with component (B), and then contacting a mixture of component (A) and component (B), (vi) A method of contacting component (S) with component (B), then with component (B), and then with a mixture of component (A) and component (B). These are some examples. If multiple types of component (B) are used, those components (B) may be the same or different. Of the above methods, (i), (ii), (iii) and (iv) are preferred.

[0148] In each of the methods described above regarding the contact sequence configuration, the presence of component (G) in the steps involving contact between component (S) and component (B), and in the steps involving contact between component (S) and component (A), suppresses fouling during the polymerization reaction and improves the particle properties of the resulting polymer. As component (G), a compound having a polar functional group can be used, and nonionic surfactants are preferred, with polyalkylene oxide blocks, higher aliphatic amides, polyalkylene oxides, polyalkylene oxide alkyl ethers, alkyldiethanolamines, polyoxyalkylene alkylamines, glycerin fatty acid esters, and N-acyl amino acids being more preferred. These may be used individually or in combination of two or more.

[0149] Examples of solvents used in preparing the olefin polymerization catalyst according to the present invention include inert hydrocarbon solvents, specifically aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; or mixtures thereof. Depending on the type of olefin to be polymerized, the olefin itself may also be used as the solvent.

[0150] During the contact between component (B) and component (S), chemical bonding occurs through the reaction between the reaction sites in component (B) and component (S), forming a contact product between component (B) and component (S). The contact time between component (B) and component (S) is usually 1 minute to 20 hours, preferably 30 minutes to 10 hours, and the contact temperature is usually -50 to 200°C, preferably -20 to 120°C. If the initial contact between component (B) and component (S) is carried out too quickly, the reaction heat and reaction energy will cause component (S) to disintegrate, degrading the morphology of the resulting solid catalyst component. When this is used in polymerization, poor polymer morphology often makes continuous operation difficult. Therefore, in the initial contact between component (B) and component (S), it is preferable to contact them at a lower temperature to suppress reaction heat, or to control the reaction heat and react at a rate that allows the initial contact temperature to be maintained. The same applies when component (B) and component (S) are brought into contact, and then component (B) is brought into contact again. The contact weight ratio between component (B) and component (S) (weight of component (B) / weight of component (S)) can be arbitrarily selected, but a higher contact weight ratio allows for contact with more component (A), thereby improving the catalytic activity per unit weight of the solid catalyst component.

[0151] The contact weight ratio of component (B) to component (S) [= weight of component (B) / weight of component (S)] is preferably 0.05 to 3.0, and particularly preferably 0.1 to 2.0. When the contact material of component (B) and component (S) is brought into contact with component (A), the contact time is usually 1 minute to 20 hours, preferably 1 minute to 10 hours, and the contact temperature is usually in the range of -50 to 200°C, preferably -50 to 100°C.

[0152] Component (B-1) is used in such an amount that the molar ratio [(B-1) / M] of component (B-1) to the total transition metal atoms (M) in component (A) is typically 0.01 to 100,000, preferably 0.05 to 50,000. Component (B-2) is used in such an amount that the molar ratio [(B-2) / M] of component (B-2) (in terms of aluminum atoms) to the total transition metal atoms (M) in component (A) is typically 10 to 500,000, preferably 20 to 100,000. Component (B-3) is used in an amount such that the molar ratio [(B-3) / M] of component (B-3) to the total transition metal atoms (M) in component (A) is usually 1 to 10, preferably 1 to 5. The ratio of component (B) to the total transition metal atoms (M) in component (A) can be determined by inductively coupled plasma atomic emission spectrometry (ICP).

[0153] For olefin polymerization, the olefin polymerization catalyst according to the present invention can be used as is, but it can also be used after prepolymerizing the olefin polymerization catalyst with an olefin to form a prepolymerized solid catalyst component. The prepolymerization solid catalyst component can be prepared by prepolymerizing an olefin (e.g., ethylene) in an inert hydrocarbon solvent in the presence of the olefin polymerization catalyst according to the present invention. This can be carried out by batch, semi-continuous, or continuous methods, and can be performed under reduced pressure, atmospheric pressure, or pressurized pressure. Furthermore, it is desirable that the prepolymerization produces 0.01 to 1000 g, preferably 0.1 to 800 g, and more preferably 0.2 to 500 g of the prepolymerization solid catalyst component per gram of the solid catalyst component.

[0154] The prepolymerization solid catalyst component, generated in an inert hydrocarbon solvent, may be separated from the suspension and then resuspended in an inert hydrocarbon to introduce an olefin (e.g., ethylene) into the resulting suspension. Alternatively, the olefin (e.g., ethylene) may be introduced after drying. The prepolymerization temperature is -20 to 80°C, preferably 0 to 60°C, and the prepolymerization time is 0.5 to 100 hours, preferably 1 to 50 hours. For prepolymerization, an olefin mainly composed of ethylene is preferably used.

[0155] The solid catalyst components used for prepolymerization can be any of those already described without limitation. Additionally, component (B) may be used as needed, and the organoaluminum compound [B-1a] represented by the general formula (B-1a) is particularly preferred. When component (B) is used, it is used in an amount such that the molar ratio (Al / M) of aluminum atoms (Al) in component (B) to transition metal atoms (M) in the transition metal compound [A] is 0.1 to 10000, preferably 0.5 to 5000.

[0156] The concentration of the olefin polymerization catalyst according to the present invention in the prepolymerization system is preferably 1 to 1000 grams / liter, and more preferably 10 to 500 grams / liter, in terms of the olefin polymerization catalyst / polymerization volume ratio. During prepolymerization, component (G) may be present for the purpose of suppressing fouling or improving particle properties. Furthermore, to improve the fluidity of the prepolymerization solid catalyst component and to suppress the generation of heat spots, sheeting, and polymer clumps during polymerization, component (G) may be brought into contact with the prepolymerization solid catalyst component that has been produced by prepolymerization.

[0157] The temperature at which the above component (G) is brought into contact is usually -50 to 50°C, preferably -20 to 50°C, and the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 10 hours. When contacting the olefin-based polymerization catalyst according to the present invention with component (G), component (G) is used in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, and more preferably 0.4 to 5 parts by weight, per 100 parts by weight of the olefin-based polymerization catalyst according to the present invention.

[0158] The mixing contact between the olefin-based polymerization catalyst and component (G) according to the present invention can be carried out in an inert hydrocarbon solvent, and examples of inert hydrocarbon solvents are the same as those described above. In the method for producing olefin polymers according to the present invention, a dried prepolymerization solid catalyst component (hereinafter also referred to as "dried prepolymerization catalyst") can be used as the catalyst for olefin polymerization. The drying of the prepolymerization solid catalyst component is usually carried out after removing hydrocarbons, which are the dispersion medium, from the obtained suspension of the prepolymerization catalyst by filtration or the like.

[0159] The prepolymerization solid catalyst component is dried by maintaining it at a temperature of 70°C or lower, preferably in the range of 20 to 50°C, under the flow of an inert gas. The volatile component content of the resulting dried prepolymerization catalyst is preferably 2.0% by weight or less, preferably 1.0% by weight or less. A lower volatile component content is preferable, and there is no particular lower limit, but practically, it is 0.001% by weight. The drying time is usually 1 to 48 hours, depending on the drying temperature.

[0160] The aforementioned dried prepolymerization catalyst has excellent fluidity, allowing it to be stably supplied to the polymerization reactor. Furthermore, using the aforementioned dried prepolymerization catalyst eliminates the need to introduce the solvent used for suspension into the gas-phase polymerization system, thus enabling stable polymerization.

[0161] [Method for producing olefin polymers] The method for producing olefin polymers according to the present invention is characterized by polymerizing an olefin in the presence of the olefin polymerization catalyst of the present invention. A preferred embodiment of the method for producing olefin polymers of the present invention is a method for producing ethylene polymers, in which ethylene is polymerized in the presence of the olefin polymerization catalyst of the present invention, or ethylene is polymerized with an olefin having 3 to 20 carbon atoms.

[0162] When the method for producing an olefin polymer of the present invention is a method for producing an ethylene polymer, the ethylene content in the ethylene polymer is preferably 70 mol% or more (assuming the total monomer units are 100 mol%).

[0163] Polymerization methods include liquid-phase polymerization methods such as solution polymerization and suspension polymerization, and gas-phase polymerization methods, with suspension polymerization and gas-phase polymerization methods being preferred. Examples of inert hydrocarbon media used in liquid-phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof.

[0164] When polymerizing olefins (e.g., ethylene) using the olefin polymerization catalyst according to the present invention, component (A) is typically 1 × 10⁻¹⁶ per liter of reaction volume. -12 ~1 × 10 -1 Moles, preferably 1 × 10⁻⁶ -8 ~1 × 10 -2 It is used in an amount that is equivalent to a mole. In addition, component (B) is used, preferably the compound represented by the general formula (B-1a) or component (B-2).

[0165] When polymerizing olefins (e.g., ethylene), the polymerization temperature has a lower limit of 0°C, preferably 40°C, and particularly preferably 60°C. Higher temperatures are advantageous in terms of heat removal and other aspects in industrial-scale production. The upper limit is usually 200°C, preferably 170°C, and the polymerization pressure is usually atmospheric pressure ~100 kgf / cm². 2Preferably at atmospheric pressure ~50 kgf / cm² 2 That is the case. Polymerization reactions can be carried out using batch, semi-continuous, or continuous methods. Furthermore, polymerization can be divided into two or more stages with different reaction conditions.

[0166] The molecular weight of the olefin polymer obtained by the method for producing olefin polymers according to the present invention can be adjusted by introducing hydrogen into the polymerization system or by changing the polymerization temperature. During polymerization, component (G) can be added for the purpose of suppressing fouling or improving particle properties.

[0167] When the method for producing an olefin polymer of the present invention is a method for producing an ethylene polymer, the monomer supplied to the polymerization reaction is either ethylene alone or ethylene and an olefin having 3 to 20 carbon atoms. Specific examples of olefins having 3 to 20 carbon atoms include α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, as well as cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

[0168] Furthermore, small amounts of styrene, vinylcyclohexane, dienes, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc., or polar monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid, etc., may be supplied within the limits that do not impair the effects of the present invention.

[0169] According to the method for producing olefin polymers of the present invention, ethylene polymers having numerous long-chain branches can be produced with high catalytic activity using a single transition metal compound. In the method for producing olefin polymers of the present invention, the inventors hypothesize that the transition metal compound [A] plays both a role in generating macromonomers, which are polymers having vinyl terminus, and a role in copolymerizing these macromonomers competitively with the polymerization of ethylene and α-olefins, as the mechanism by which long-chain branches are introduced into the ethylene polymer. Furthermore, by using the transition metal compound [A] in contact with a support [S], which is an optional component, the concentration of macromonomers near the reaction site of the transition metal compound [A] can be increased, making it possible to produce ethylene polymers with more long-chain branches.

[0170] Furthermore, according to the method for producing olefin polymers of the present invention, even higher molecular weight ethylene polymers can be produced with higher catalytic activity. R on the 1-indenyl ring in the transition metal compound [A] 9 ~R 12 It is thought that the polymer's molecular weight increased because the steric hindrance caused by the substituents suppressed the chain transfer reaction of the growing polymer chain. Also, the R on the 1-indenyl ring 9 ~R 12 It is believed that the catalytic activity has been significantly improved compared to conventional compounds for reasons such as the unique stereostructure due to substituents, or the steric effects resulting from said stereostructure, which can further increase the macromonomer concentration near the reaction site of the transition metal compound [A], or the central metal being covered by substituents, which increases thermal stability.

[0171] [Olefin polymers] The ethylene polymer produced by the method for producing olefin polymers according to the present invention has many long-chain branches of appropriate length and preferably satisfies the following requirements (1) to (4). (1) The melt flow rate (MFR) at 190°C under a 2.16 kg load is 0.1 g / 10 min or more and 50 g / 10 min or less, preferably 0.5 g / 10 min or more and 30 g / 10 min or less; (2) Density is 875 kg / m³ 3 More than 965kg / m 3 Preferably 885 kg / m 3 More than 945kg / m 3 The following: (3) Zero shear viscosity [η0(P)] at 200°C and the weight-average molecular weight raised to the power of 6.8 (Mw) measured by the GPC-viscosity detector method (GPC-VISCO). 6.8 ) ratio, η0 / Mw 6.8 However, 0.03 × 10 -30 The above 7.5 × 10 -30 The following is preferably 0.03 × 10 -30 The above 5.0 x 10 -30 The following: (4) The intrinsic viscosity [η](dl / g) measured in decalin at 135°C and the weight-average molecular weight raised to the power of 0.776 (Mw) measured by the GPC-viscosity detector method (GPC-VISCO). 0.776 The ratio of [η] / Mw 0.776 However, 0.90 × 10 -4 The above 1.65 × 10 -4 The following is preferably 0.90 × 10 -4 The above 1.55 × 10 -4 The following applies:

[0172] The melt flow rate (MFR) value is strongly dependent on the molecular weight; a smaller MFR corresponds to a larger molecular weight, and a larger MFR corresponds to a smaller molecular weight. It is also known that the molecular weight of ethylene polymers is determined by the hydrogen-to-ethylene ratio (hydrogen / ethylene) within the polymerization system (e.g., Kazuo Soga et al., "Catalytic Olefin Polymerization," Kodansha Scientific, 1990, p. 376). Therefore, it is possible to increase or decrease the melt flow rate (MFR) of ethylene polymers by increasing or decreasing the hydrogen / ethylene ratio.

[0173] The density value mentioned above depends on the α-olefin content of the ethylene polymer; the lower the α-olefin content, the higher the density, and the higher the α-olefin content, the lower the density. It is also known that the α-olefin content in an ethylene polymer is determined by the composition ratio of α-olefin to ethylene (α-olefin / ethylene) in the polymerization system (e.g., Walter Kaminsky, Makromol. Chem. 193, p. 606 (1992)). Therefore, by increasing or decreasing the α-olefin / ethylene ratio, ethylene polymers with densities within the above range can be produced.

[0174] Requirements (3) and (4) above are both well-known indicators relating to long-chain branching, and for their significance, refer to, for example, Japanese Patent Publication No. 2006-233207, International Publication No. 2006 / 080578, International Publication No. 2013 / 099927, etc.

[0175] The olefin polymer (e.g., ethylene polymer) produced by the present invention may be pelletized.

[0176] The olefin polymer (e.g., ethylene polymer) produced by the present invention may contain, as necessary, additives such as weather-resistant stabilizers, heat-resistant stabilizers, antistatic agents, anti-slip agents, anti-blocking agents, anti-fogging agents, lubricants, pigments, dyes, nucleating agents, plasticizers, anti-aging agents, hydrochloric acid absorbers, and antioxidants, provided that the objectives of the present invention are not impaired.

[0177] The olefin polymers (e.g., ethylene polymers) produced by the present invention can be processed by general film molding, blow molding, injection molding, and extrusion molding. Examples of molded articles obtained by processing olefin polymers (e.g., ethylene polymers) produced by the present invention include films, blow-molded infusion bags, blow-molded bottles, gasoline tanks, extruded tubes, pipes, tear-off caps, injection-molded products such as daily necessities, fibers, and large molded products by rotational molding.

[0178] The film obtained by processing the olefin polymer (e.g., ethylene polymer) produced by the present invention is suitable for various packaging films such as liquid packaging bags, liquid soup packaging bags, liquid paper containers, laminated raw materials, special-shaped liquid packaging bags (standing pouches, etc.), standard bags, heavy bags, wrap films, sugar bags, oil packaging bags, food packaging films, protective films, infusion bags, agricultural materials, etc. It can also be laminated with a base material such as nylon or polyester to be used as a multilayer film. [Examples]

[0179] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0180] [Measurement of various physical properties] The method for measuring the physical properties of ethylene polymers is shown below. <Density (D)> The strands obtained during MFR measurement were heat-treated at 100°C for 30 minutes, then left at room temperature for 1 hour before being measured using the density gradient tube method.

[0181] <Number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), molecular weight distribution (Mw / Mn, Mz / Mw)> The following measurements were taken using an Agilent GPC-VISCO PL-GPC220 GPC detector. Two Agilent PLgel Olexis columns were used for analysis, and a differential refractometer and a 3-capillary viscometer were used as detectors. The column temperature was set to 145°C, o-dichlorobenzene was used as the mobile phase, the flow rate was 1.0 ml / min, and the sample concentration was 0.1 wt%. Standard polystyrene used was manufactured by Tosoh Corporation. Molecular weight was calculated by determining the measured viscosity from the viscometer and refractometer, and the number-average molecular weight (Mn), weight-average molecular weight (Mw), Z-average molecular weight (Mz), and molecular weight distribution (Mw / Mn, Mz / Mw) were determined from the measured universal calibration.

[0182] <Synthesis of transition metal compound [A]> [Synthesis Example 1-1] In a thoroughly dried and argon-purged 100 mL reactor, 3.44 g (20.0 mmol) of 4,5,6,7-tetramethyl-1-H-indene obtained by the method described in "Organometallics 2007, 26, 5869." and 25 mL of tetrahydrofuran were charged. 13.2 mL of n-butyllithium solution (hexane solution, 1.59 M, 21.0 mmol) was added, and the mixture was stirred at room temperature for 2 hours. This reaction mixture was slowly added to a 25 mL dilution of 15.5 mL (120 mmol) of dimethylsilyl dichloride in n-hexane under cooling to -78°C, and the mixture was stirred for 18 hours while returning to room temperature. After removing the solvent and unreacted dimethylsilyl dichloride from the reaction mixture by distillation, 20 mL of tetrahydrofuran and 2.20 mL (20.0 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. In a thoroughly dried and argon-purged 200 mL reactor, 1.07 g (42.6 mmol) of magnesium was charged, and the mixture was vigorously stirred for 30 minutes under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and one iodine tablet and 25 mL of tetrahydrofuran were charged and stirred. A 25 mL diluted solution of 4.29 g (22.0 mmol) of 2-bromoindene in tetrahydrofuran was added dropwise (after adding 1.0 mL, the mixture was heated under reflux using a dryer until the iodine color disappeared, and the remaining solution was added dropwise after the reaction started). After the dropwise addition was complete, the mixture was stirred at room temperature for 2 hours. This solution was added dropwise to the previously diluted reaction residue solution cooled to -78 °C, and the mixture was stirred for 19 hours while slowly returning to room temperature. Saturated ammonium chloride aqueous solution was added, the soluble components were extracted with n-hexane, the obtained fraction was washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtering out the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography, yielding 3.90 g (57% yield) of the target product (hereinafter referred to as compound (A-1L)) shown in the following formula (A-1L) as an isomer mixture. 1H NMR(270MHz,CDCl3)δ 7.45-7.44(1H,d,J=7.1Hz,Ar-H),7.40-7.38(1H,d,J=7.3Hz,Ar-H),7.28-7.27(1H,m,Ar- H),7.20-7.17(1H,t,Ar-H),7.07(1H,s,C=CH-C),6.96-6.95(1H,d,C=CH-C),6.53-6.51(1H ,d,C=CH-C),3.82(1H,s,Si-CH),3.40-3.30(2H,m,C-CH2-C),2.36(3H,s,-CH3),2.25(3H,s ,-CH3),2.21(3H,s,-CH3),2.17(3H,s,-CH3),0.14(3H,s,Si-CH3),0.02(3H,s,Si-CH3)ppm

[0183] [ka]

[0184] [Example 1A] In a thoroughly dried and argon-purged 100 mL reactor, 0.86 g (2.5 mmol) of compound (A-1L) obtained in Synthesis Example 1-1, 25 mL of toluene, and 0.40 mL of tetrahydrofuran were charged and stirred. To this solution, 3.2 mL of n-butyllithium solution (hexane solution, 1.58 M, 5.0 mmol) was added at room temperature, and stirring was continued in an oil bath at 40°C for 3 hours. This solution was cooled to 0°C, 0.58 g (2.5 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After removing the solvent from the reaction mixture, dichloromethane was added to the resulting solid to prepare a suspension, and insoluble matter was removed using Celite on a glass filter. The obtained solution was concentrated under reduced pressure, and then a suspension was prepared by adding n-hexane. Insoluble matter was filtered off using a glass filter, and the residue was dried under reduced pressure to obtain 0.46 g (yield 37%) of a yellow powdery compound represented by the following formula (A-1) (hereinafter referred to as compound (A-1)). 1H NMR(270MHz,CDCl3)δ 7.51-7.45(2H,m,J=7.1Hz,Ar-H),7.26-7.23(1H,m,J=7.3Hz,Ar-H),7.19- 7.15(1H,m,Ar-H),7.07-7.06(1H,d,Ind-H),6.38-6.37(1H,d,Ind-H),6.0 8-6.07(1H,d,Ind-H),5.97-5.96(1H,d,Ind-H),2.50(3H,s,-CH3),2.34(3 H,s,-CH3),2.27(6H,s,-CH3),1.07(3H,s,Si-CH3),0.94(3H,s,Si-CH3)ppm FD-Mass Spectrometry (M + ):504

[0185] [ka]

[0186] [Synthesis Example 2-1] In a thoroughly dried and argon-purged 500 mL reactor, 12.6 g (0.29 mol) of sodium hydride and 80 mL of dimethoxyethane were charged. To this, 21.0 g (0.13 mol) of 4,7-dimethylindanone synthesized by the method described in WO2016 / 188999 and 80 mL of dimethoxyethane were added dropwise, and the mixture was stirred for 10 minutes. The reaction mixture was cooled to 0°C, and 32.7 mL (0.29 mol) of iodobutane was added dropwise, and the mixture was stirred at room temperature for 15 hours. Water was added, and the soluble components were extracted with ethyl acetate. The resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the residue obtained by distillation was purified by silica gel column chromatography to obtain 22.5 g (yield 63%) of the target product shown in the following formula (A-2a) (hereinafter referred to as compound (A-2a)). 1 H NMR(270MHz,CDCl3)δ 7.25-7.23(1H,d,Ar-H),7.03-7.01(1H,d,Ar-H),2.97-2.94(2H,m,C-CH2-C),2.68-2.65(2H,m,C-CH2-C),2.60(3H,s,-CH3),2.30(3H,s,-CH3)ppm

[0187] [ka]

[0188] [Synthesis Example 2-2] In a thoroughly dried and argon-purged 1 L reactor, 107.86 g (1.65 mol) of zinc powder, 208.4 mL (1.65 mol) of trimethylsilyl chloride, 360 mL of methanol, and 120 mL of methylene chloride were charged. After cooling to 0°C, 22.5 g (0.82 mol) of compound (A-2a) obtained in Synthesis Example 2-1 was added dropwise, and the mixture was stirred at 0°C for 1 hour. Saturated sodium hydroxide aqueous solution was added, and the soluble components were extracted with methylene chloride. The resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the residue obtained by distillation was purified by silica gel column chromatography, yielding 16.9 g (yield 79%) of the target product shown in the following formula (A-2b) (hereinafter referred to as compound (A-2b)). 1 H NMR(270MHz,CDCl3)δ 7.24-7.23(1H,d,Ar-H),7.02-7.00(1H,d,Ar-H),2.81(2H,s,C-CH2-C),2.60(3H,s,-CH3),2.30( 3H,s,-CH3),1.61-1.55(4H,m,C-CH2-C),1.27-1.04(8H,m,C-CH2-C),0.88-0.82(6H,m,-CH3)ppm

[0189] [ka]

[0190] [Synthesis Example 2-3] In a thoroughly dried and argon-purged 200 mL reactor, 17.8 g (68.9 mmol) of compound (A-2b) obtained in Synthesis Example 2-2, 6.6 mL (68.9 mmol) of 3-chloropropionyl chloride, and 85 mL of methylene chloride were added. The mixture was cooled to 0°C, and 20.7 g (155 mmol) of aluminum chloride was gradually added. The mixture was stirred at room temperature for 18 hours. The reaction mixture was poured into concentrated hydrochloric acid and ice, and the soluble components were extracted with methylene chloride. The resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the residue obtained by distillation was purified by silica gel column chromatography to obtain 13.0 g (yield 61%) of the target product shown in the following formula (A-2c) (hereinafter referred to as compound (A-2c)). 1 H NMR(270MHz,CDCl3)δ 2.90-2.88(2H,t,C-CH2-C),2.72-2.64(6H,m,C-CH2-C),2.50(3H,s,-CH3),2.17(3H,s,- CH3),1.45-1.41(4H,m,C-CH2-C),1.31-1.22(8H,m,C-CH2-C),0.91-0.88(6H,m,-CH3)ppm

[0191] [ka]

[0192] [Synthesis Example 2-4] In a thoroughly dried and argon-purged 200 mL reactor, 3.16 g (83.4 mmol) of sodium borohydride, 45 mL of tetrahydrofuran, and 15 mL of methanol were added. After cooling to 0°C, 13.0 g (41.7 mmol) of compound (A-2c) obtained in Synthesis Example 2-3 was added dropwise, and the mixture was stirred at room temperature for 2 hours. 1 N hydrochloric acid was added, and the soluble components were extracted with ethyl acetate. The resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the residue obtained by distillation was purified by silica gel column chromatography to obtain 9.9 g (80% yield) of the target product shown in the following formula (A-2d) (hereinafter referred to as compound (A-2d)). 1H NMR(270MHz,CDCl3)δ 6.98-6.95(1H,m,Ar-H),6.47-6.45(1H,m,Ar-H),3.27(2H,s,Ar-CH2-Ar),2.72-2.71(4H,d,C-CH2-C),2.29(3H, s,-CH3),2.21(3H,s,-CH3),1.47-1.43(4H,m,C-CH2-C),1.27-1.25(8H,m,C-CH2-C),0.91-0.88(6H,m,-CH3)ppm

[0193]

change

[0194] [Synthesis example 2-5] In a thoroughly dried and argon-purged 100 mL reactor, 5.93 g (20.0 mmol) of the compound (A-2d) obtained in Synthesis Example 2-4 and 25 mL of tetrahydrofuran were charged. 13.2 mL of n-butyllithium solution (hexane solution, 1.59 M, 21.0 mmol) was added, and the mixture was stirred at room temperature for 2 hours. This reaction mixture was slowly added to a 25 mL diluted solution of 12.0 mL (100 mmol) of dimethylsilyl dichloride in n-hexane under cooling to -78°C, and the mixture was stirred for 18 hours while returning to room temperature. After removing the solvent and unreacted dimethylsilyl dichloride from the reaction mixture, 20 mL of tetrahydrofuran and 2.20 mL (20.0 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue. In a thoroughly dried and argon-purged 200 mL reactor, 1.07 g (42.6 mmol) of magnesium was charged, and the mixture was vigorously stirred for 30 minutes under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and one iodine tablet and 25 mL of tetrahydrofuran were charged and stirred. A 25 mL diluted solution of 4.29 g (22.0 mmol) of 2-bromoindene in tetrahydrofuran was added dropwise (after adding 1.0 mL, the mixture was heated under reflux using a dryer until the iodine color disappeared, and the remaining solution was added dropwise after the reaction started). After the dropwise addition was complete, the mixture was stirred at room temperature for 2 hours. This solution was added dropwise to the previously diluted reaction residue solution cooled to -78 °C, and the mixture was stirred for 19 hours while slowly returning to room temperature. Saturated ammonium chloride aqueous solution was added, the soluble components were extracted with n-hexane, the obtained fraction was washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtering out the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography, yielding 1.99 g (21% yield) of the target product (hereinafter referred to as compound (A-2L)) shown in the following formula (A-2L) as an isomer mixture. 1H NMR(270MHz,CDCl3)δ 7.44-7.42(1H,d,J=7.1Hz,Ar-H),7.39-7.37(1H,d,J=7.3Hz,Ar-H),7.27-7.24(1H,m,Ar-H),7.19-7.16(1H, m,Ar-H),7.03(1H,d,C=CH-C),6.92-6.91(1H,d,C=CH-C),6.52-6.50(1H,d,C=CH-C),3.77(1H,m,Si-CH),3.3 4-3.19(2H,m,C-CH2-C),2.70-2.65(4H,m,C-CH2-C),2.25(3H,s,-CH3),2.09(3H,s,-CH3),1.48-1.41(4H,m, C-CH2-C),1.31-1.23(8H,m,C-CH2-C),0.93-0.87(6H,m,-CH3),0.14(3H,s,Si-CH3),0.08(3H,s,Si-CH3)ppm

[0195] [ka]

[0196] [Example 2A] In a thoroughly dried and argon-purged 100 mL reactor, 1.36 g (2.9 mmol) of compound (A-2L) obtained in Synthesis Example 2-5, 29 mL of toluene, and 0.47 mL of tetrahydrofuran were charged and stirred. To this solution, 3.69 mL of n-butyllithium solution (hexane solution, 1.57 M, 5.8 mmol) was added at room temperature, and stirring was continued in an oil bath at 40°C for 3 hours. This solution was cooled to 0°C, 0.68 g (2.9 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After the solvent of the reaction mixture was removed by distillation, dichloromethane was added to the obtained solid to prepare a suspension, and insoluble matter was removed using Celite on a glass filter. The obtained solution was concentrated under reduced pressure, and then a suspension was prepared by adding n-hexane. Insoluble matter was filtered off using a glass filter, and the residue was dried under reduced pressure to obtain 0.79 g (43% yield) of a yellow powdery compound represented by the following formula (A-2) (hereinafter referred to as compound (A-2)). 1H NMR(270MHz,CDCl3)δ 7.50-7.45(2H,m,J=8.3Hz,Ar-H),7.26-7.15(2H,m,J=8.2Hz,Ar-H),7.04-7.03(1H,d,Ind-H), 6.35-6.34(1H,d,J=3.5Hz,Ind-H),6.08(1H,d,J=6.6Hz,Ind-H),5.99(1H,d,J=6.8Hz,Ind-H),2 .78-2.65(4H,m,C-CH2-C),2.40(3H,s,-CH3),2.25(3H,s,-CH3),1.45-1.37(4H,m,C-CH2-C),1. 26-1.24(8H,m,C-CH2-C),1.06(3H,s,Si-CH3),0.92(3H,s,Si-CH3),0.91-0.88(6H,m,-CH3)ppm FD-Mass Spectrometry (M + ):626

[0197] [ka]

[0198] [Comparative Example 1A] A yellow powdery compound represented by the following formula (A'-1) (dimethylsilylene(2-indenyl)(4,7-dimethyl-1-indenyl)zirconium dichloride; hereinafter referred to as compound (A'-1)) was synthesized by the method described in Synthesis Example 7-2 of Japanese Patent Publication No. 2019-059933.

[0199] [ka]

[0200] [Example 1] <Preparation of Solid Catalyst Component (X-1)> Using a 270L reactor with a stirrer, under a nitrogen atmosphere, silica gel (manufactured by Fuji Silicia Chemical Co., Ltd., with a cumulative 50% particle size of 70 μm and specific surface area of ​​340 m² as the solid support [S]) was used. 2 / g, pore volume: 1.3cm 310 kg of solid support [S-1] (1 / g, dried at 250°C for 10 hours) was suspended in 77 L of toluene and then cooled to 0-5°C. 19.4 L of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atoms) was added dropwise to this suspension as component (B) over 30 minutes. During this time, the system temperature was maintained at 0-5°C. Next, these were brought into contact at 0-5°C for 30 minutes, then the system temperature was raised to 95°C over 1.5 hours, and contact continued at 95°C for 4 hours. After that, the temperature was lowered to room temperature, the supernatant was removed by decantation, and the mixture was washed twice with toluene to prepare a total volume of 115 L of toluene slurry. A portion of the obtained slurry was taken and analyzed, and the solid content concentration was 122.6 g / L and the Al concentration was 0.612 mol / L. Next, 30 mL of toluene and 1.63 mL of the slurry obtained above (0.2 g solid weight) were charged into a 200 mL stirred reactor that had been thoroughly purged with nitrogen under a nitrogen atmosphere. Then, 5.0 μmol of the toluene solution of compound (A-1) obtained in Example 1A was added as Zr, and the mixture was brought into contact with the reactor at a system temperature of 20-25°C for 1 hour. The supernatant was then removed by decantation, and the mixture was washed twice with hexane. This prepared a slurry of solid catalyst component (X-1) with a total volume of 40 mL.

[0201] <Production of ethylene polymers> In a 1-liter stainless steel autoclave with a sufficient nitrogen purging, 500 ml of heptane was added under a nitrogen atmosphere, and then ethylene was passed through to saturate the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30.0 mg of the solid catalyst component (X-1) in slurry form were charged in. ,workman The polymerization reaction was carried out in a ethylene solution at 80°C and 0.8 MPaG for 90 minutes. After filtering the resulting polymer, it was vacuum-dried at 80°C for 10 hours to obtain 109.8 g of ethylene polymer. The catalytic activity was 10,980 g-PE / g-solid catalyst component. . Conclusion The results are shown in Table 9.

[0202] [Example 2] <Preparation of Solid Catalyst Component (X-2)> A slurry of the solid catalyst component (X-2) was prepared in the same manner as in Example 1, except that compound (A-2) obtained in Example 2A was used instead of compound (A-1) in Example 1.

[0203] <Production of ethylene polymers> In a 1-liter stainless steel autoclave with a sufficient nitrogen purging, 500 ml of heptane was added under a nitrogen atmosphere, and then ethylene was passed through to saturate the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30.0 mg of the solid catalyst component (X-2) in slurry form were charged in. ,workman The polymerization reaction was carried out in a ethylene solution at 80°C and 0.8 MPaG for 90 minutes. After filtering the resulting polymer, it was vacuum-dried at 80°C for 10 hours to obtain 187.7 g of ethylene polymer. The catalytic activity was 6,250 g-PE / g-solid catalyst component. . Conclusion The results are shown in Table 9.

[0204] [Comparative Example 1] <Preparation of Solid Catalyst Component (X-3)> A slurry of the solid catalyst component (X-3) was prepared in the same manner as in Example 1, except that compound (A'-1) obtained in Comparative Example 1A was used instead of compound (A-1) in Example 1.

[0205] <Production of ethylene polymers> In a 1-liter stainless steel autoclave with a sufficient nitrogen purging, 500 ml of heptane was added under a nitrogen atmosphere, and then ethylene was passed through to saturate the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 250 mg of the solid catalyst component (X-3) in slurry form were charged in. The temperature was then raised to 80°C and the pressure to 0.8 MPaG with ethylene, and the polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum-dried at 80°C for 10 hours to obtain 80.0 g of ethylene-based polymer. The catalytic activity was 2,670 g-PE / g-solid catalyst component. The results are shown in Table 9.

[0206] [Table 9]

[0207] Examples 1 and 2, which used the transition metal compound [A] (a crosslinked (2-indenyl)(1-indenyl) type compound having a specific substituent on the 1-indenyl ring) of the present invention, showed higher catalytic activity compared to Comparative Example 1, which used a crosslinked (2-indenyl)(1-indenyl) type compound without the substituent. In addition, the molecular weight (Mw) of Examples 1 and 2 increased compared to Comparative Example 1.

Claims

1. A transition metal compound [A] represented by the following general formula [1]. 【Chemistry 1】 (In general formula [1], M is a zirconium atom or a hafnium atom, n is an integer from 1 to 4 selected such that the transition metal compound [A] is electrically neutral. X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group (R α). If n is 2 or more, the multiple groups represented by X may be the same or different from each other, and may be bonded to each other to form a ring. The oxygen-containing group (R α) is a methoxy group, an ethoxy group, an iso-propoxy group, or a tert-butoxy group. Q is a carbon or silicon atom. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 13 and R 14 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms (R β ), an oxygen-containing group having 1 to 20 carbon atoms (R γ ) or a nitrogen-containing group having 1 to 20 carbon atoms (R δ ), The silicon-containing group (R β) is a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-iso-propylsilylphenyl group, or a 3,5-bis(trimethylsilyl)phenyl group. The oxygen-containing group (R γ) is a methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group, phenoxy group, dimethoxymethyl group, dioxolanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, benzofuryl group, or dibenzofuryl group. The nitrogen-containing group (R δ) is an amino group, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a dimethylaminophenyl group, a 3,5-dimethyl-4-dimethylaminophenyl group, a 3,5-di-iso-propyl-4-dimethylaminophenyl group, a jurolidinyl group, a tetramethyljurolidinyl group, a pyrrolidinylphenyl group, a pyrrolyl group, a pyridyl group, a carbazolyl group, or an imidazolyl group. R 9 , R 10 , R 11 , R 12 These are, independently, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms (R ε), or a nitrogen-containing group having 1 to 20 carbon atoms (R ζ), The oxygen-containing group (R ε) is synonymous with the oxygen-containing group (R γ), The nitrogen-containing group (R ζ) is synonymous with the nitrogen-containing group (R δ), R 1 ~R 6 Adjacent substituents may bond to each other to form a ring which may also have substituents. R 10 and R 11 These may be bonded to each other to form a ring which may have substituents. R 13 and R 14 These elements may be bonded to each other to form a ring containing Q, and this ring may have substituents.

2. In the above general formula [1], A transition metal compound [A] according to claim 1, wherein Q is a silicon atom.

3. In the above general formula [1], R 1 and R 6 However, the transition metal compound [A] according to claim 2 is a hydrogen atom.

4. In the above general formula [1], R 2 ~R 5 and R 8 However, the transition metal compound [A] according to claim 3 is a hydrogen atom.

5. In the above general formula [1], R 9 ~R 12 The transition metal compound [A] according to claim 4, wherein each of these is independently a hydrocarbon group having 1 to 20 carbon atoms, a methoxy group, an iso-propoxy group, a tert-butoxy group, an allyloxy group, or a phenoxy group.

6. In the above general formula [1], R 9 ~R 12 However, each is independently a hydrocarbon group having 1 to 20 carbon atoms, a methoxy group, an iso-propoxy group, a tert-butoxy group, an allyloxy group, or a phenoxy group. R 10 and R 11 The transition metal compound [A] according to claim 4, wherein the compounds do not bond to each other to form a ring.

7. In the above general formula [1], R 9 ~R 12 However, each is independently a hydrocarbon group having 1 to 20 carbon atoms, a methoxy group, an iso-propoxy group, a tert-butoxy group, an allyloxy group, or a phenoxy group. R 10 and R 11 The transition metal compound [A] according to claim 4, wherein the compounds are bonded to each other to form a ring which may have substituents.

8. A catalyst for olefin polymerization comprising the transition metal compound [A] described in any one of claims 1 to 7.

9. Furthermore, [B][B-1] organometallic compounds, [B-2] Organic aluminum oxy compounds, and The catalyst for olefin polymerization according to claim 8, comprising at least one compound selected from the group consisting of [B-3] compounds that react with a transition metal compound [A] to form an ion pair.

10. A method for producing an olefin polymer, comprising the step of polymerizing an olefin in the presence of the olefin polymerization catalyst described in claim 8.

11. A method for producing an olefin polymer according to claim 10, wherein the step of polymerizing the olefin is a step of homopolymerizing ethylene or a step of copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms.

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