Method for producing catalyst for olefin polymerization and method for producing ethylene-based polymer

Abstract

To provide a method for producing a catalyst for olefin polymerization and the like that enable easy production of an ethylene-based polymer with large bulk density.SOLUTION: A method for producing a catalyst for olefin polymerization comprising: a transition metal compound (A) of formula [1]; a compound (B); and a solid carrier (C), wherein the method includes contacting the compound (A) with the solid carrier (C) at a temperature lower than 20°C.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing an olefin polymerization catalyst and a method for producing an ethylene polymer. [Background technology]

[0002] A large number of studies have been conducted and many publications have been published on catalysts for olefin polymerization that contain a solid support component and a transition metal compound component. As such olefin polymerization catalysts, for example, Patent Documents 1 to 4 disclose supported olefin polymerization catalysts prepared by a specific method, which contain a predetermined carrier component and a predetermined metallocene compound component, as catalysts capable of producing polymers having desired physical properties with high polymerization activity. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-059933 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-306929 [Patent Document 3] Special Publication No. 2012-503689 [Patent Document 4] Japanese Patent Application Publication No. 8-027237 Summary of the Invention [Problem to be solved by the invention]

[0004] Olefin polymerization methods described in Patent Documents 1 to 4 include slurry polymerization, bulk polymerization, and gas-phase polymerization, but in any of these methods, if the bulk density of the produced polymer is low, the supported catalyst tends to be partially pulverized during polymerization, resulting in the generation of fine powder. If fine powder is generated during polymerization, the fine powder may adhere to the inner wall of the reactor, causing fouling, clogging of transfer piping, or deterioration of fluidity in gas-phase polymerization, which may lead to other problems.

[0005] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a method for producing an olefin polymerization catalyst and a method for producing ethylene polymer particles, which can easily produce an ethylene polymer having a high bulk density. [Means for solving the problem]

[0006] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration examples, and have thus completed the present invention. An example of the configuration of the present invention is as follows.

[0007] [1] A transition metal compound (A) represented by the following general formula [1], at least one compound (B) selected from the group consisting of an organometallic compound (B-1), an organoaluminum oxy compound (B-2), and a compound (B-3) that reacts with the transition metal compound (A) to form an ion pair; a solid carrier (C) which is an inorganic compound; A method for producing an olefin polymerization catalyst, comprising: A method for producing an olefin polymerization catalyst, comprising the step of contacting the transition metal complex (A) with the solid support (C) at a temperature below 20°C.

[0008] [ka] (In the general formula [1], M' is a transition metal atom of Group 4 of the periodic table, n' is an integer of 1 to 4 selected so that the transition metal compound (A) is electrically neutral; X' represents a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and 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, and when n is 2 or more, the multiple groups represented by X may be the same or different and may be bonded to each other to form a ring; Q' is an atom of Group 14 of the periodic table, R' 1 , R' 2 , R' 3 , R' 4 , R' 5 , R' 6 , R' 7 , R' 8 , R' 9 and R' 10 each independently represents 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' 1 ~R' 8 Adjacent substituents among these may be bonded to each other to form a ring which may have a substituent, R' 9 and R' 10 may be bonded to each other to form a ring containing Q', and this ring may have a substituent.

[0009] [2] The method for producing an olefin polymerization catalyst according to the above [1], wherein the transition metal compound (A) is represented by the following general formula [2]:

[0010] [ka] (In the general formula [2], M is a transition metal atom of Group 4 of the periodic table, n is an integer of 1 to 4 selected so that the transition metal compound (A) is electrically neutral; X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and 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, and when n is 2 or more, the multiple groups represented by X may be the same or different and may be bonded to each other to form a ring; Q is an atom of group 14 of the periodic table, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 each independently represents 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 1 ~R 6 Adjacent substituents among R may be bonded to each other to form a ring which may have a substituent, 7 ~R 12 Adjacent substituents among these may be bonded to each other to form a ring which may have a substituent, R 13 and R 14 may be bonded to each other to form a ring containing Q, and this ring may have a substituent.

[0011] [3] In the general formula [2], M is a zirconium atom or a hafnium atom, X's each independently represent 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 ~R6 and R 7 ~R 14 are each independently 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.

[0012] [4] In the general formula [2], Q is a silicon atom, R 1 and R 6 is a hydrogen atom, R 2 ~R 5 and R 7 ~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, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms.

[0013] [5] The method for producing an olefin polymerization catalyst according to any one of the above [1] to [4], wherein the solid support (C) is a porous oxide.

[0014] [6] A method for producing an ethylene-based polymer, comprising polymerizing ethylene or polymerizing ethylene and an olefin having from 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst obtained by the method for producing an olefin polymerization catalyst according to any one of the above items [1] to [5].

[0015] [7] The method for producing an ethylene polymer according to [6] above, wherein the polymerization temperature is 0°C or higher. [Effects of the Invention]

[0016] According to the method for producing an olefin polymerization catalyst and the method for producing an ethylene polymer according to the present invention, an ethylene polymer having a high bulk density can be produced. If the bulk density of the produced ethylene polymer is high, it is expected that fouling during production will be suppressed, and that the blockage of transfer piping will be prevented, thereby enabling safe and stable operation of production equipment, and that operability will be improved, particularly in gas phase polymerization. DETAILED DESCRIPTION OF THE INVENTION

[0017] The process for producing an olefin polymerization catalyst according to the present invention will be described in more detail below. [Method of producing an olefin polymerization catalyst] The method for producing an olefin polymerization catalyst according to the present invention is characterized in that the olefin polymerization catalyst comprises a transition metal compound (A) represented by general formula [1], at least one compound (B) selected from the group consisting of organometallic compounds (B-1), organoaluminum oxy-compounds (B-2), and compounds (B-3) that react with the transition metal compound (A) to form an ion pair, and a solid support (C) that is an inorganic compound, and the method comprises a step of contacting the transition metal complex (A) with the solid support (C) at a temperature below 20°C.

[0018] <Olefin polymerization catalyst> The olefin polymerization catalyst obtained by the method for producing an olefin polymerization catalyst according to the present invention (hereinafter also referred to as "the present olefin polymerization catalyst") comprises a transition metal compound (A) (hereinafter also referred to as "component (A)"), a compound (B) (hereinafter also referred to as "component (B)"), and a solid support (C) (hereinafter also referred to as "component (C)").

[0019] [Transition metal compound (A)] The transition metal compound (A) is represented by the following general formula [1].

[0020] [ka]

[0021] M', n', X' In the 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.

[0022] n' is an integer of 1 to 4, preferably 1 or 2, and more preferably 2, selected so that the transition metal compound (A) is electrically neutral.

[0023] X' is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and 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. X' is preferably a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group.

[0024] When n' is 2 or more, the multiple X' may be the same or different and may be bonded to each other to form a ring. When multiple rings are present, the rings may be the same or different.

[0025] The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., preferably a chlorine atom or a bromine atom, more preferably a chlorine atom.

[0026] Examples of the hydrocarbon group include: linear or branched alkyl groups such as methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl (butan-2-yl), tert-butyl (2-methylpropan-2-yl), isobutyl (2-methylpropyl), pentan-2-yl, 2-methylbutyl, isopentyl (3-methylbutyl), neopentyl (2,2-dimethylpropyl), cyamyl (1,2-dimethylpropyl), isohexyl (4-methylpentyl), 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, thexyl (2,3-dimethylbut-2-yl), and 4,4-dimethylpentyl; Vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), allenyl group (propa-1,2-dien-1-yl group), but-3-en-1-yl group, crotyl group (but-2-en-1-yl group), but-3-en-2-yl group, methallyl group (2-methylallyl group), buta-1,3-dienyl group, pentaerythritol group, linear or branched alkenyl groups or unsaturated double bond-containing groups such as pent-4-en-1-yl, pent-3-en-1-yl, pent-2-en-1-yl, iso-pentenyl (3-methylbut-3-en-1-yl), 2-methylbut-3-en-1-yl, pent-4-en-2-yl, and prenyl (3-methylbut-2-en-1-yl); linear or branched alkynyl groups or unsaturated triple bond-containing groups such as ethynyl, prop-2-yn-1-yl, and propargyl (prop-1-yn-1-yl) groups; Aromatic-containing 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-isopropylbenzyl group), 2,4,6-tri-isopropylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, and benzhydryl group (diphenylmethyl group); cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cycloheptatrienyl, norbornyl, norbornenyl, 1-adamantyl, and 2-adamantyl; Examples of aromatic substituents include a phenyl group, a tolyl group (methylphenyl group), a xylyl group (dimethylphenyl group), a mesityl group (2,4,6-trimethylphenyl group), a cumenyl group (isopropylphenyl group), a duryl group (2,3,5,6-tetramethylphenyl group), a 2,6-di-isopropylphenyl group, a 2,4,6-tri-isopropylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, a naphthyl group, a biphenyl group, a tert-phenyl group, a binaphthyl group, an acenaphthalenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, and a ferrocenyl group.

[0027] Among the hydrocarbon groups, a methyl group, an isobutyl group, a neopentyl group, a cyamyl group, a benzyl group, a phenyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group are preferred.

[0028] Examples of the halogen-containing group include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, and a hexachloroantimonate anion. Among the halogen-containing groups, a pentafluorophenyl group is preferred.

[0029] Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, a tris(trimethylsilyl)silyl group, a trimethylsilylmethyl group, etc. Among the silicon-containing groups, a trimethylsilylmethyl group is preferred.

[0030] Examples of the oxygen-containing group include methoxy, ethoxy, n-propoxy, isopropoxy, allyloxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, benzyloxy, methoxymethoxy, phenoxy, 2,6-dimethylphenoxy, 2,6-diisopropylphenoxy, 2,6-ditert-butylphenoxy, 2,4,6-trimethylphenoxy, 2,4,6-triisopropylphenoxy, acetoxy, pivaloyloxy, benzoyloxy, trifluoroacetoxy, perchlorate anion, and periodate anion. Among the oxygen-containing groups, methoxy, ethoxy, isopropoxy, and tert-butoxy are preferred.

[0031] Examples of the sulfur-containing group include mesyl group (methanesulfonyl group), phenylsulfonyl group, tosyl group (p-toluenesulfonyl group), triflyl group (trifluoromethanesulfonyl group), nonaflyl group (nonafluorobutanesulfonyl group), mesylate group (methanesulfonate group), tosylate group (p-toluenesulfonate group), triflate group (trifluoromethanesulfonate group), and nonaflate group (nonafluorobutanesulfonate group).Among the sulfur-containing groups, triflate (trifluoromethanesulfonate) is preferred.

[0032] Examples of the nitrogen-containing group include an amino group, a cyano group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholyl group, a pyrrolyl group, a bistriflylimide group, etc. Among the nitrogen-containing groups, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a pyrrolyl group, and a bistriflylimide group are preferred.

[0033] The phosphorus-containing group may, for example, be a hexafluorophosphate anion.

[0034] Examples of the boron-containing group 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 (each R independently represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

[0035] Examples of the aluminum-containing group include: [ka] (M' represents M' in the general formula [1]) and is a group represented by AlR4 (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

[0036] Examples of the conjugated diene derivative group include a 1,3-butadienyl group, an isoprenyl group (2-methyl-1,3-butadienyl group), a piperylenyl group (1,3-pentadienyl group), a 2,4-hexadienyl group, a 1,4-diphenyl-1,3-pentadienyl group, a cyclopentadienyl group, and a metallocyclopentene group.

[0037] Examples of neutral ligands capable of coordinating with lone electron pairs 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 organic phosphorus compounds such as triphenylphosphine, tricyclohexylphosphine, and tri-tert-butylphosphine.

[0038] Q' In the general formula [1], 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, more preferably a silicon atom.

[0039] 《R' 1 ~R' 10 》 In the general formula [1], R' 1 , R' 2 , R' 3 , R' 4 , R' 5 , R' 6 , R' 7 , R' 8 , R' 9 and R' 10 are each 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.

[0040] R' 1 ~R' 10 Examples of the hydrocarbon group having 1 to 40 carbon atoms as X' include hydrocarbon groups having 1 to 20 carbon atoms, and more specific examples include the specific hydrocarbon groups given as examples of X' above.

[0041] The hydrocarbon group having 1 to 40 carbon atoms is preferably a hydrocarbon group having 1 to 20 carbon atoms (excluding aromatic hydrocarbon groups) or an aromatic hydrocarbon group having 6 to 40 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms is preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms also includes a substituent having an aromatic structure such as an arylalkyl group.

[0042] Examples of the hydrocarbon group having 1 to 40 carbon atoms include: Methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decanyl, 1-undecanyl, 1-dodecanyl, 1-eicosanyl, isopropyl, sec-butyl, tert-butyl, isobutyl, pentan-2-yl, 2-methylbutyl, isopentyl, neopentyl, tert-pentyl (1,1-dimethylpropyl), cyamyl, pentan-3-yl, 2-methylpentyl, 3-methylpentyl, isohexyl, 1,1-dimethylbutyl (2-methylpentan-2-yl), 3-methylpentyl linear or branched alkyl groups having 1 to 40 carbon atoms, such as hexyl, 2-methylpentan-2-yl, 4-methylpentan-2-yl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, thexyl, 3-methylpentan-3-yl, 3,3-dimethylbut-2-yl, hexane-3-yl, 2-methylpentan-3-yl, heptan-4-yl, 2,4-dimethylpentan-2-yl, 3-ethylpentan-3-yl, 4,4-dimethylpentyl, 4-methylheptan-4-yl, 4-propylheptan-4-yl, 2,3,3-trimethylbutan-2-yl, and 2,4,4-trimethylpentan-2-yl; Vinyl group, allyl group, propenyl group, isopropenyl group, allenyl group, but-3-en-1-yl group, crotyl group, but-3-en-2-yl group, methallyl group, but-1,3-dienyl group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, isopentenyl group, 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, prenyl group, 2-methyl-but-2-en-1 -yl group, pent-3-en-2-yl group, 2-methyl-but-3-en-2-yl group, pent-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-but-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hex-5-en-1-yl group, hex-4-en-1-yl group, hex-3-en -1-yl group, hex-2-en-1-yl group, 4-methyl-pent-4-en-1-yl group, 3-methyl-pent-4-en-1-yl group, 2-methyl-pent-4-en-1-yl group, hex-5-en-2-yl group, 4-methyl-pent-3-en-1-yl group, 3-methyl-pent-3-en-1-yl group, 2,3-dimethyl-but-2-en-1-yl group, 2-methylpent-4-en-2-yl group, 3-ethylpent-1-en linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, such as a hexa-3-yl group, a hexa-3,5-dien-1-yl group, a hexa-2,4-dien-1-yl group, a 4-methylpenta-1,3-dien-1-yl group, a 2,3-dimethyl-buta-1,3-dien-1-yl group, a hexa-1,3,5-trien-1-yl group, a 2-(cyclopentadienyl)propan-2-yl group, or a 2-(cyclopentadienyl)ethyl group; Ethynyl group, prop-2-yn-1-yl group, propargyl group, but-1-yn-1-yl group, but-2-yn-1-yl group, but-3-yn-1-yl group, pent-1-yn-1-yl group, pent-2-yn-1-yl group, pent-3-yn-1-yl group, pent-4-yn-1-yl group, 3-methyl-but-1-yn-1-yl group, pent-3-yn-2-yl group, 2-methyl-but-3-yn-1-yl group linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, such as a pent-4-yn-2-yl group, a hex-1-yn-1-yl group, a 3,3-dimethyl-but-1-yn-1-yl group, a 2-methyl-pent-3-yn-2-yl group, a 2,2-dimethyl-but-3-yn-1-yl group, a hex-4-yn-1-yl group, or a hex-5-yn-1-yl group; Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-isopropylbenzyl 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-triphenylpropan-2-yl group, 1,1-diphenylethyl group, 1,1-diphenylpropyl group, 1,1-diphenyl-but-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-isopropylphenyl)ethyl group, 2-(4-tert-butylphenyl)ethyl group, 2-(3,(5-di-tert-butylphenyl)ethyl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group (3-phenylallyl group), neophyl group (2-methyl-2-phenylpropyl group), 3-methyl-3-phenylbutyl group, 2-methyl-4-phenylbutan-2-yl group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(tetrahydro-1-indacenyl)propan-2-yl group, (tetrahydro-1-indacenyl ) Aromatic-containing 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-azulenyl)propan-2-yl group, (1-azulenyl)diphenylmethyl group, and 2-(1-azulenyl)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-methylcyclohex Sil 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 group -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]octan-1-yl group, bicyclo[2.2.2]octan-2-yl group, 1-adamantyl group, 2-adamantyl group, 1-(2-methyladamantyl), 1-(3-methyladamantyl), 1-(4-methyladamantyl) cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, such as 1-(2-phenyladamantyl), 1-(3-phenyladamantyl), 1-(4-phenyladamantyl), 1-(3,5-dimethyladamantyl), 1-(3,5,7-trimethyladamantyl), 1-(3,5,7-triphenyladamantyl), pentalenyl group, indenyl group, fluorenyl group, indacenyl group, tetrahydroindacenyl group, benzoindenyl group, and azulenyl group; Examples of aromatic substituents having 6 to 40 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a duryl group, a 2,6-di-isopropylphenyl group, a 2,4,6-tri-isopropylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, an allylphenyl group, a (but-3-en-1-yl)phenyl group, a (but-2-en-1-yl)phenyl group, a methallylphenyl group, a prenylphenyl group, a 4-adamantylphenyl group, a 3,5-di-adamantylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, an acenaphthalenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, and a ferrocenyl group.

[0043] Among the linear or branched alkyl groups having 1 to 40 carbon atoms, a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, a 1-heptyl group, a 1-octyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a pentan-3-yl group, an isohexyl group, a 1,1-dimethylbutyl group, a 3,3-dimethylbutyl group, a thexyl group, a 3-methylpentan-3-yl group, a heptane-4-yl group, a methyl group, a ...methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group, a methyl group Preferred are methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, isopropyl, tert-butyl, neopentyl, 2,4-dimethylpentan-2-yl, and 2,4,4-trimethylpentan-2-yl groups.

[0044] Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, a vinyl group, an allyl group, a but-3-en-1-yl group, a crotyl group, a methallyl group, a pent-4-en-1-yl group, a prenyl group, a penta-1,4-dien-3-yl group, a hex-5-en-1-yl group, a 2-methylpent-4-en-2-yl group, a 2-(cyclopentadienyl)propan-2-yl group, a 2-(cyclopentadienyl)ethyl group, and the like are preferred, and a vinyl group, an allyl group, a but-3-en-1-yl group, a pent-4-en-1-yl group, a prenyl group, and a hex-5-en-1-yl group are more preferred.

[0045] Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, an ethynyl group, a prop-2-yn-1-yl group, a propargyl group, a but-2-yn-1-yl group, a but-3-yn-1-yl group, a penta-3-yn-1-yl group, a penta-4-yn-1-yl group, a 3-methyl-but-1-yn-1-yl group, a 3,3-dimethyl-but-1-yn-1-yl group, a hex-4-yn-1-yl group, a hex-5-yn-1-yl group, and the like are preferred, and a propa-2-yn-1-yl group, a propargyl group, a but-2-yn-1-yl group, and a but-3-yn-1-yl group are more preferred.

[0046] Among the aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, 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-tert-butyl ... Preferred are a 2-(3,5-di-tert-butylphenyl)ethyl group, a 2-(3,5-di-tert-butylphenyl)ethyl group, a styryl group, a 2-methyl-1-phenylpropan-2-yl group, a 3-phenylpropyl group, a cinnamyl group, a neophyl group, a cyclopentadienyldiphenylmethyl group, a 2-(1-indenyl)propan-2-yl group, a (1-indenyl)diphenylmethyl group, a 2-(1-indenyl)ethyl group, a 2-(9-fluorenyl)propan-2-yl group, a (9-fluorenyl)diphenylmethyl group, and a 2-(9-fluorenyl)ethyl group, and more preferred are a benzyl group, a benzhydryl group, a cumyl group, a 1,1-diphenylethyl group, a trityl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a cinnamyl group.

[0047] Among the above-mentioned cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a 1-methylcyclopentyl group, a 1-allylcyclopentyl group, a 1-benzylcyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 1-methylcyclohexyl group, a 1-allylcyclohexyl group, a 1-benzylcyclohexyl group, a cycloheptyl group, a cycloheptenyl group, a cycloheptatrienyl group, a 1-methylcycloheptyl group, a 1-allylcycloheptyl group, a 1-benzyl A cycloheptyl group, a cyclooctyl group, a cyclooctenyl group, a cyclooctadienyl group, a 4-cyclohexyl-tert-butyl group, a norbornyl group, a 2-methylbicyclo[2.2.1]heptan-2-yl group, a bicyclo[2.2.2]octan-1-yl group, a 1-adamantyl group, a 2-adamantyl group, a pentalenyl group, an indenyl group, a fluorenyl group, and the like are preferred, and a cyclopentyl group, a cyclopentenyl group, a 1-methylcyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group are more preferred.

[0048] Among the aromatic substituents having 6 to 40 carbon atoms, a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 2,6-di-isopropylphenyl group, a 2,4,6-tri-isopropylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, an allylphenyl group, a prenylphenyl group, a 4-adamantylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, a phenanthryl group, an anthracenyl group, a ferrocenyl group, and the like are preferred, and a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 2,6-di-isopropylphenyl group, a 2,4,6-tri-isopropylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, an allylphenyl group, a 4-adamantylphenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, and an anthracenyl group are more preferred.

[0049] Examples of the halogen-containing group include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoropropyl group, a 3,3,3-trifluoropropyl group, a nonafluorobutyl group, a 4,4,4-trifluorobutyl group, a dodecafluorohexyl group, a 6,6,6-trifluorohexyl group, a chlorophenyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a di-tert-butyl-fluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a trifluoromethoxyphenyl group, a bistrifluoromethoxyphenyl group, a trifluoromethylthiophenyl group, a bistrifluoromethylthiophenyl group, a fluorobiphenyl group, a difluorobiphenyl group, Examples thereof include a trifluorobiphenyl group, a tetrafluorobiphenyl group, a pentafluorobiphenyl group, a di-tert-butyl-fluorobiphenyl group, a trifluoromethylbiphenyl group, a bistrifluoromethylbiphenyl group, a trifluoromethoxybiphenyl group, a bistrifluoromethoxybiphenyl group, a trifluoromethyldimethylsilyl group, a trifluoromethoxy group, a pentafluoroethoxy group, a fluorophenoxy group, a difluorophenoxy group, a trifluorophenoxy group, a pentafluorophenoxy group, a di-tert-butyl-fluorophenoxy group, a trifluoromethylphenoxy group, a bistrifluoromethylphenoxy group, a trifluoromethoxyphenoxy group, a bistrifluoromethoxyphenoxy group, a difluoromethylenedioxyphenyl group, a bistrifluoromethylphenyliminomethyl group, and a trifluoromethylthio group.

[0050] Among the halogen-containing groups, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a trifluoromethoxyphenyl group, a pentafluorobiphenyl group, a trifluoromethylbiphenyl group, a bistrifluoromethylbiphenyl group, a trifluoromethoxy group, a pentafluorophenoxy group, a bistrifluoromethylphenoxy group, a bistrifluoromethylphenoxy group, a difluoromethylenedioxyphenyl group, and a trifluoromethylthio group are preferred, and a trifluoromethyl group, a fluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a pentafluorobiphenyl group, a trifluoromethoxy group, and a pentafluorophenoxy group are more preferred.

[0051] Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, a tris(trimethylsilyl)silyl group, a cyclopentadienyldimethylsilyl group, a di-n-butyl(cyclopentadienyl)silyl group, a cyclopentadienyldiphenylsilyl group, an indenyldimethylsilyl group, and a di-n-butyl(indenyl)silyl group. )silyl group, indenyldiphenylsilyl group, fluorenyldimethylsilyl group, di-n-butyl(fluorenyl)silyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-isopropylsilylphenyl group, 4-tert-butyldiphenylsilylphenyl group, 4-triphenylsilylphenyl group, 4-tris(trimethylsilyl)silylphenyl group, 3,5-bis(trimethylsilyl)phenyl group, and the like.

[0052] Among the silicon-containing groups, a trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, a cyclopentadienyldimethylsilyl group, a cyclopentadienyldiphenylsilyl group, an indenyldimethylsilyl group, an indenyldiphenylsilyl group, a fluorenyldimethylsilyl group, a fluorenyldiphenylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-isopropylsilylphenyl group, a 4-triphenylsilylphenyl group, and a 3,5-bis(trimethylsilyl)phenyl group are preferred, and a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-isopropylsilylphenyl group, and a 3,5-bis(trimethylsilyl)phenyl group are more preferred.

[0053] Examples of the oxygen-containing group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a methallyloxy group, a prenyloxy group, a benzyloxy group, a methoxymethoxy group, a methoxyethoxy group, a phenoxy group, a naphthoxy group, a toluyloxy group, an isopropylphenoxy group, an allylphenoxy group, a tert-butylphenoxy group, a methoxyphenoxy group, an isopropoxyphenoxy group, an allyloxyphenoxy group, a biphenyloxy group, a binaphthyloxy group, a methoxymethyl group, an allyloxymethyl group, a benzyloxymethyl group, a phenoxymethyl group, a methoxyethyl group, an allyloxyethyl group, a benzyloxyethyl group, a phenoxyethyl group, a methoxypropyl group, an aliphatic acid ... Examples of such groups include an allyloxypropyl group, a benzyloxypropyl group, a phenoxypropyl group, a methoxyvinyl group, an allyloxyvinyl group, a benzyloxyvinyl group, a phenoxyvinyl group, a methoxyallyl group, an allyloxyallyl group, a benzyloxyallyl group, a phenoxyallyl group, a dimethoxymethyl group, a di-iso-propoxymethyl group, a dioxolanyl group, a tetramethyldioxolanyl group, a dioxanyl group, a methoxyphenyl group, an iso-propoxyphenyl group, an allyloxyphenyl group, a phenoxyphenyl group, a methylenedioxyphenyl group, a 3,5-dimethyl-4-methoxyphenyl group, a 3,5-di-tert-butyl-4-methoxyphenyl group, a furyl group, a methylfuryl group, a tetrahydrofuryl group, a pyranyl group, a tetrahydropyranyl group, a furofuryl group, a benzofuryl group, and a dibenzofuryl group.

[0054] Among the oxygen-containing groups, a methoxy group, an ethoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a tert-butoxy group, a prenyloxy group, a benzyloxy group, a phenoxy group, a naphthoxy group, a toluyloxy group, an iso-propylphenoxy group, an allylphenoxy group, a tert-butylphenoxy group, a methoxyphenoxy group, a biphenyloxy group, a binaphthyloxy group, an allyloxymethyl group, a benzyloxymethyl group, a phenoxymethyl group, a methoxyethyl group, a methoxyallyl group, a benzyloxyallyl group, a phenoxyallyl group, a dimethoxymethyl group, a dioxolanyl group, a tetramethyldioxolanyl group, a dioxanyl group, a dimethyldioxanyl group, a methoxyphenyl group, an iso-propoxyphenyl group, an allyloxymethyl ... Preferred are a phenyl group, a phenoxyphenyl group, a methylenedioxyphenyl group, a 3,5-dimethyl-4-methoxyphenyl group, a 3,5-di-tert-butyl-4-methoxyphenyl group, a furyl group, a methylfuryl group, a tetrahydropyranyl group, a furofuryl group, a benzofuryl group, and a dibenzofuryl group, and more preferred are a methoxy group, an iso-propoxy group, a tert-butoxy group, an allyloxy group, a phenoxy group, a dimethoxymethyl group, a dioxolanyl group, a methoxyphenyl group, an iso-propoxyphenyl group, an allyloxyphenyl group, a phenoxyphenyl group, a 3,5-dimethyl-4-methoxyphenyl group, a 3,5-di-tert-butyl-4-methoxyphenyl group, a furyl group, a methylfuryl group, a benzofuryl group, and a dibenzofuryl group.

[0055] Examples of the nitrogen-containing group include an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a diallylamino group, a didecylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholyl group, an azepinyl group, a dimethylaminomethyl group, a dibenzylaminomethyl group, a pyrrolidinylmethyl group, a dimethylaminoethyl group, a benzylaminomethyl group, a benzylaminoethyl group, a pyrrolidinylethyl group, a dimethylaminovinyl group, a benzylaminovinyl group, a pyrrolidinylvinyl group, a dimethylaminopropyl group, a benzylaminopropyl group, a pyrrolidinylpropyl group, a dimethylaminoallyl group, a benzylaminoallyl group, a pyrrolidinylallyl group, an aminophenyl group, a dimethylaminophenyl group, a 3,5-dimethyl-4-dimethylaminophenyl group, Examples of such groups include a 3,5-di-iso-propyl-4-dimethylaminophenyl group, a julolidinyl group, a tetramethyljulolidinyl group, a pyrrolidinylphenyl group, a pyrrolylphenyl group, a pyridylphenyl group, a quinolylphenyl group, an isoquinolylphenyl group, an indolinylphenyl group, an indolylphenyl group, a carbazolylphenyl group, a di-tert-butylcarbazolylphenyl group, a pyrrolyl group, a methylpyrrolyl group, a phenylpyrrolyl group, a pyridyl group, a quinolyl group, a tetrahydroquinolyl group, an isoquinolyl group, a tetrahydro-isoquinolyl group, an indolyl group, an indolinyl group, a carbazolyl group, a di-tert-butylcarbazolyl group, an imidazolyl group, a dimethylimidazolidinyl group, a benzimidazolyl group, an oxazolyl group, an oxazolidinyl group, and a benzoxazolyl group.

[0056] Among the nitrogen-containing groups, an amino group, a dimethylamino group, a diethylamino group, an allylamino group, a benzylamino group, a dibenzylamino group, a pyrrolidinyl group, a piperidinyl group, a morpholyl group, a dimethylaminomethyl group, a benzylaminomethyl group, a pyrrolidinylmethyl group, a dimethylaminoethyl group, a pyrrolidinylethyl group, a dimethylaminopropyl group, a pyrrolidinylpropyl group, a dimethylaminoallyl group, a pyrrolidinylallyl group, an aminophenyl group, a dimethylaminophenyl group, a 3,5-dimethyl-4-dimethylaminophenyl group, a 3,5-di-iso-propyl-4-dimethylaminophenyl group, a julolidinyl group, a tetramethyljulolidinyl group, a pyrrolidinylphenyl group, a pyrrolylphenyl group, a carbazolylphenyl group, a di-tert-butylcarbazolyl group, A phenyl group, a pyrrolyl group, a pyridyl group, a quinolyl group, a tetrahydroquinolyl group, an isoquinolyl group, a tetrahydro-isoquinolyl group, an indolyl group, an indolinyl group, a carbazolyl group, a di-tert-butylcarbazolyl group, an imidazolyl group, a dimethylimidazolidinyl group, a benzimidazolyl group, an oxazolyl group, an oxazolidinyl group, a benzoxazolyl group, and the like are preferred, and 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-isopropyl-4-dimethylaminophenyl group, a julolidinyl group, a tetramethyljulolidinyl group, a pyrrolidinylphenyl group, a pyrrolyl group, a pyridyl group, a carbazolyl group, and an imidazolyl group are more preferred.

[0057] Examples of the sulfur-containing group include a methylthio group, an ethylthio group, a benzylthio group, a phenylthio group, a naphthylthio group, a methylthiomethyl group, a benzylthiomethyl group, a phenylthiomethyl group, a naphthylthiomethyl group, a methylthioethyl group, a benzylthioethyl group, a phenylthioethyl group, a naphthylthioethyl group, a methylthiovinyl group, a benzylthiovinyl group, a phenylthiovinyl group, a naphthylthiovinyl group, a methylthiopropyl group, a benzylthiopropyl group, a phenylthiopropyl group, a naphthylthiopropyl group, a methylthioallyl group, a benzylthioallyl group, a phenyl Examples thereof include a thioallyl group, a naphthylthioallyl group, a mercaptophenyl group, a methylthiophenyl group, a thienylphenyl group, a methylthienylphenyl group, a benzothienylphenyl group, a dibenzothienylphenyl group, a benzodithienylphenyl group, a thienyl group, a tetrahydrothienyl group, a methylthienyl group, a thienofuryl group, a thienothienyl group, a benzothienyl group, a dibenzothienyl group, a thienobenzofuryl group, a benzodithienyl group, a dithiolanyl group, a dithianyl group, an oxathiolanyl group, an oxathianyl group, a thiazolyl group, a benzothiazolyl group, and a thiazolidinyl group.

[0058] Among the sulfur-containing groups, a thienyl group, a methylthienyl group, a thienofuryl group, a thienothienyl group, a benzothienyl group, a dibenzothienyl group, a thienobenzofuryl group, a benzodithienyl group, a thiazolyl group, and a benzothiazolyl group are preferred.

[0059] R' 1 ~R' 4 Adjacent substituents (e.g., R' 1 and R' 2 , R' 2 and R' 3 , R' 3 and R' 4) may be bonded to each other to form a ring which may have a substituent. In this case, the ring formed is preferably a 5- to 8-membered ring which is fused to the pentadienyl ring moiety and which is made of a saturated hydrocarbon (excluding the hydrocarbon of the pentadienyl ring moiety) or an unsaturated hydrocarbon which may have a substituent. When multiple rings are present, these may be the same or different. Although not particularly limited as long as the effects of the present invention are achieved, the ring is more preferably a 6-membered ring, and in this case, the structure formed by combining the ring and the pentadienyl ring moiety of the mother nucleus is preferably, for example, a substituted indenyl ring.

[0060] R' 5 ~R' 8 Adjacent substituents (e.g., R' 5 and R' 6 , R' 6 and R' 7 , R' 7 and R' 8 ) may be bonded to each other to form a ring which may have a substituent. In this case, the ring formed is preferably a 5- to 8-membered ring which is fused to the pentadienyl ring moiety and which is made of a saturated hydrocarbon (excluding the hydrocarbon of the pentadienyl ring moiety) or an unsaturated hydrocarbon which may have a substituent. When multiple rings are present, these may be the same or different. Although not particularly limited as long as the effects of the present invention are achieved, the ring is more preferably a 6-membered ring, and in this case, the structure formed by combining the ring and the pentadienyl ring moiety of the mother nucleus is preferably, for example, a substituted indenyl ring.

[0061] R' 9 and R' 10 may be bonded to each other to form a ring containing Q'. In this case, the ring formed is preferably a 3- to 8-membered saturated or unsaturated ring which may have a substituent. Although there are no particular limitations as long as the effects of the present invention are achieved, the ring is preferably a 4- to 6-membered ring, and in this case, R' 9 and R' 10and Q′ together include, for example, a substituted cyclobutane ring, a substituted cyclopentane ring, a substituted fluorene ring, a substituted silacyclobutane (siletane) ring, a substituted silacyclopentane (silorane) ring, a substituted silacyclohexane (silinane), and a substituted silafluorene ring, of which a substituted cyclopentane ring, a substituted silacyclobutane ring, and a substituted silacyclopentane ring are preferred.

[0062] R' 1 and R' 4 are each independently 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.

[0063] R' 2 ~R' 3 , R' 5 ~R' 10 are each independently 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.

[0064] R' 2 and R' 3 and R' 7 and R' 8 are preferably bonded to each other to form a ring which may have a substituent, and the ring formed in this case is a 6-membered ring which is condensed to the pentadienyl ring moiety and which may have a substituent, and R' 2 and R' 3 forms a substituted 2-indenyl ring, and R' 7 and R' 8 It is particularly preferred that: forms a substituted 1-indenyl ring.

[0065] In addition, R' 5 and R' 8 In at least one of the oxygen-containing group, nitrogen-containing group, or sulfur-containing group, the heterocyclic aromatic group described below may be a heterocyclic aromatic group.

[0066] <Preferred embodiment of transition metal compound (A)> The transition metal compound (A) is preferably a transition metal compound (A-1) represented by the following general formula [2].

[0067] [ka]

[0068] M, n, X, Q In the general formula [2], M, n, X, and Q have the same meanings as M', n', X', and Q' in the general formula [1], respectively.

[0069] 《R 1 ~R 14 》 In the general formula [1], R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each 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.

[0070] R 1 ~R 14 In the general formula [1], the hydrocarbon group having 1 to 40 carbon atoms, the halogen-containing group, the silicon-containing group, the oxygen-containing group, the nitrogen-containing group or the sulfur-containing group is R' 1 ~R' 10 Examples of the groups include hydrocarbon groups having 1 to 40 carbon atoms, halogen-containing groups, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups, and sulfur-containing groups, which are given as examples of the groups.

[0071] R 1 ~R 6Adjacent 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 6 ) may be bonded to each other to form a ring which may have a substituent. In this case, the ring formed is preferably a 5- to 8-membered ring which is fused to the indenyl ring moiety and which is made of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring moiety) or an unsaturated hydrocarbon which may have a substituent. When multiple rings are present, these may be the same or different. Although there are no particular limitations as long as the effects of the present invention are achieved, the ring is more preferably a 5- or 6-membered ring. In this case, examples of the structure formed by combining the ring and the indenyl ring moiety of the mother nucleus include a substituted benzoindenyl ring, a substituted tetrahydroindacene ring, and a substituted cyclopentatetrahydronaphthalene, and a substituted benzoindenyl ring and a substituted tetrahydroindacene ring are preferred.

[0072] R 7 ~R 12 Adjacent substituents (e.g., R 7 and R 8 , R 8 and R 9 , R 9 and R 10 , R 10 and R 11 , and R 11 and R 12) may be bonded to each other to form a ring which may have a substituent. In this case, the ring formed is preferably a 5- to 8-membered ring which is fused to the indenyl ring moiety and which is made of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring moiety) or an unsaturated hydrocarbon which may have a substituent. When multiple rings are present, these may be the same or different. Although not particularly limited as long as the effects of the present invention are achieved, the ring is more preferably a 5- or 6-membered ring. In this case, examples of the structure formed by combining the ring and the indenyl ring moiety of the mother nucleus include a substituted benzoindenyl ring, a substituted tetrahydroindacene ring, a substituted cyclopentatetrahydronaphthalene, a substituted tetrahydrofluorene ring, and a substituted fluorene ring, and a substituted benzoindenyl ring and a substituted tetrahydroindacene ring are preferred.

[0073] R 13 and R 14 may be bonded to each other to form a ring containing Q. In this case, the ring formed is preferably a 3- to 8-membered saturated or unsaturated ring which may have a substituent. Although there are no particular limitations as long as the effects of the present invention are achieved, the ring is preferably a 4- to 6-membered ring, and in this case, R 13 and R 14 and Q together include, for example, a substituted cyclobutane ring, a substituted cyclopentane ring, a substituted fluorene ring, a substituted silacyclobutane (siletane) ring, a substituted silacyclopentane (silorane) ring, a substituted silacyclohexane (silinane), and a substituted silafluorene ring, of which a substituted cyclopentane ring, a substituted silacyclobutane ring, and a substituted silacyclopentane ring are preferred.

[0074] R 1 and R 6 are each independently 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.

[0075] R 2 ~R 5 and R 7 ~R 14are each independently 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. In addition, R 7 , R 9 and R 12 In at least one of the oxygen-containing group, nitrogen-containing group, or sulfur-containing group, the heterocyclic aromatic group described below may be a heterocyclic aromatic group.

[0076] More preferred embodiments of the transition metal compound (A) include: In the general formula [2], M is a zirconium atom or a hafnium atom, X's each independently represent 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 6 and R 7 ~R 14 and each independently represents 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.

[0077] A more preferred embodiment of the transition metal compound (A) is In the general formula [2], Q is a silicon atom, R 1 and R 6 is a hydrogen atom, R 2 ~R 5 and R 7 ~R 14 wherein each independently represents 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.

[0078] The oxygen-containing group, nitrogen-containing group, and sulfur-containing group in R7, R9, and R12 in the transition metal compound (A-2) include an optionally substituted heteroaromatic group having a five-membered ring (hereinafter also referred to as a "heterocyclic five-membered ring") backbone containing at least one atom selected from the group consisting of nitrogen, oxygen, and sulfur. Examples of the heteroaromatic group include groups represented by the following general formulas [4a] to [4h].

[0079] [ka]

[0080] In the general formulas [4a] to [4h], Ch represents an oxygen atom or a sulfur atom, and R d are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different. The wavy lines in the general formulae [4a] to [4h] indicate the bonding sites to the indenyl ring.

[0081] Examples of the hydrocarbon group having 1 to 20 carbon atoms include the above-mentioned R' 1 ~R' 10Among the hydrocarbon groups having 1 to 40 carbon atoms mentioned above as examples of the hydrocarbon group having 1 to 40 carbon atoms, those having 1 to 20 carbon atoms are exemplified, and preferred are a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, a 1-heptyl group, a 1-octyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an allyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclooctenyl group, a norbornyl group, a bicyclo[2.2.2]octan-1-yl group, a 1-adamantyl group, a 2-adamantyl group, a benzyl group, a benzhydryl group, a cumyl group, a 1,1-diphenylethyl group, a trityl group, a 2-phenylethyl group, a 3-phenylethyl group, a 2 ... Examples thereof include a propyl group, a cinnamyl group, a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 2,6-di-isopropylphenyl group, a 2,4,6-tri-isopropylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, a 4-adamantylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, a phenanthryl group, an anthracenyl group, and a ferrocenyl group, and more preferably, a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an allyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a benzyl group, a phenyl group, a tolyl group, a xylyl group, a mesityl group, a naphthyl group, a biphenyl group, and a terphenyl group.

[0082] R d are independent of each other, and adjacent R dThey may bond to each other to form a saturated or unsaturated hydrocarbon group that is fused to the 5-membered heterocyclic moiety and that may have a substituent and that, together with the atoms of the 5-membered heterocyclic moiety, constitutes a 5- to 8-membered ring. The 5- to 8-membered ring is not particularly limited as long as the effects of the present invention are achieved, but is preferably a 5- or 6-membered ring. In this case, examples of the structure formed by combining this ring with the 5-membered heterocyclic moiety of the mother 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.

[0083] Among the heterocyclic aromatic groups represented by the general formulae [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], a 2-furyl group, a 5-methyl-2-furyl group, a 2-thienyl group, and a 5-methyl-2-thienyl group are preferred.

[0084] <<Examples of transition metal compound (A)>> Specific examples of the transition metal compound (A-1), which is a preferred embodiment of the transition metal compound (A), are shown below, but the scope of the present invention is not particularly limited by these.

[0085] For convenience, the MX of the transition metal compound (A-1) n The ligand structure excluding the portion represented by (metal portion) is represented by the 2-indenyl ring portion, the 1-indenyl ring portion, and the indenyl ring portion R 1 , R 6 and R 8 Substituent, indenyl ring moiety R 2 , R 5 , R 9 , and R 12 Substituent, indenyl ring moiety R 3 , R 4 , R 10 , and R 11 Substituent, 1-indenyl ring moiety R 7 The structure of the substituent and the bridged portion is divided into seven parts. The abbreviation for the 2-indenyl ring portion is α, the abbreviation for the 1-indenyl ring portion is β, and the indenyl ring portion R 1 , R6 and R 8 The abbreviation for the substituent is γ, and the indenyl ring portion is R 2 , R 5 , R 9 , and R 12 The abbreviation of the substituent is δ, and the indenyl ring part is R 3 , R 4 , R 10 , and R 11 The abbreviation for the substituent is ε, and the 1-indenyl ring moiety is R 7 The abbreviation for the substituent is ζ, the abbreviation for the structure of the crosslinked portion is η, and the abbreviations for each substituent are shown in [Table 1] to [Table 7].

[0086] [Table 1]

[0087] [Table 2] The wavy lines in Tables 1 and 2 indicate the bonding sites with the crosslinked moieties.

[0088] [Table 3] R in Table 3 1 , R 6 and R 8 The substituents in any combination may be the same or different from one another.

[0089] [Table 4] R in Table 4 2 , R 5 , R 9 , and R 12 The substituents in any combination may be the same or different from one another.

[0090] [Table 5] R in Table 5 3 , R 4 , R10 , and R 11 The substituents in any combination may be the same or different from one another.

[0091] [Table 6]

[0092] [Table 7]

[0093] Specific examples of the metal moiety 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), 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 Hf(1,3-butadienyl), Hf(1,3-pentadienyl), Hf(2,4-hexadienyl), Hf(1,4-diphenyl-1,3-pentadienyl), Hf(CH2-Si(Me)3), Hf(OMe), Hf(OMiPr), Hf(NMe), Hf(OMs), Hf(OTs), and Hf(OTf). Here, 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, OMe is an isopropoxy group, NMe2 is a dimethylamino group, OMs is a methanesulfonate group, OTs is a p-toluenesulfonate group, and OTf is a trifluoromethanesulfonate group.

[0094] According to the above notation, the 2-indenyl ring moiety is α-1 in [Table 1], the 1-indenyl ring moiety is β-1 in [Table 2], and the indenyl ring moiety R 1 , R 6 and R 8 All of the substituents are the γ-1,2-indenyl ring moiety R in [Table 3] 2 and R 5 All of the substituents are the δ-1,2-indenyl ring moiety R in [Table 4] 3 and R 4 The substituents are all ε-1,1-indenyl ring moiety R in [Table 5] 7 The substituent is the ζ-1,1-indenyl ring moiety R in [Table 6] 9 The substituent is δ-40 in [Table 4], 1-indenyl ring moiety R 12 When the substituent is δ-3 in [Table 4], the bridging portion is η-20 in [Table 7], and the metal portion MXn is ZrCl2, the compound represented by the following formula [5] is exemplified.

[0095] [ka]

[0096] In addition, the transition metal compound (A-1) has two faces (front and back) of the indenyl ring moiety that is bonded to the central metal across the bridge. Therefore, when the 2-indenyl ring moiety does not have a symmetrical plane, two structural isomers, for example, represented by the following general formula [9a] or [9b], exist.

[0097] [ka]

[0098] Similarly, the substituent R of the bridging portion 13 and R 14 are not identical, there exist two structural isomers represented by the following general formula [10a] or [10b].

[0099] [ka]

[0100] Purification and separation of these structural isomer mixtures, or selective production of structural isomers, can be performed by known methods, and the production method is not particularly limited. Known production methods include those exemplified as the production method for the transition metal compound (A-1), as well as production methods disclosed in JP-A-10-109996, "Organometallics 1999, 18, 5347," "Organometallics 2012, 31, 4340," and JP-A-2011-502192.

[0101] Within the scope of the transition metal compound (A), the transition metal compound may be used alone or in combination of two or more, or a structural isomer mixture may be used, or a structural isomer may be used alone or in combination of two or more. As described above, according to the present invention, as the transition metal compound constituting the olefin polymerization catalyst, one or more transition metal compounds other than the transition metal compound (A) may be used in combination within the scope that does not impair the effects of the present invention. In this case, the transition metal compound (A) may be in any of the above-mentioned embodiments.

[0102] <<Method for producing transition metal compound (A)>> The transition metal compound (A) can be produced by a conventionally known method, and a typical example of the synthesis route is shown below using the transition metal compound (A-1) as an example, but the production method is not particularly limited. 1 ~R 14 , Q, M, X and n have the same meanings as those described in the above general formula [2].

[0103] The substituted indene compound as a starting material can be produced by a known method, and the production method is not particularly limited. Known production methods include those described in "Organometallics 1994, 13,954," "Organometallics 2006, 25, 1217," JP-A-2006-509059, "Bioorg.Med.Chem. 2008, 16, 7399," WO2009 / 080216, "Organometallics 2011, 30, 5744," JP-A-2011-500800, "Organometallics 2012, 31, 4962," and "Chem.Eur.J. 2012,18,4174.", JP 2012-012307 A, JP 2012-121882 A, JP 2014-196319 A, JP 2014-513735 A, JP 2015-063495 A, JP 2016-501952 A, and the like.

[0104] Of the above-mentioned substituted indene compounds, those not substituted at the 2-position can be brominated at the 2-position by the following known methods, and the production method is not particularly limited.

[0105] [ka]

[0106] In the formula (1), NBS represents N-bromosuccinimide, and PTSA represents p-toluenesulfonic acid or its monohydrate. Indene compounds have five-membered ring moiety double bond positional isomers, and a mixture of these isomers may be used. Examples of known production methods include those disclosed in JP-A-2012-121882 and JP-A-2015-063495, as well as those disclosed in JP-A-2014-111568.

[0107] The 2-brominated substituted indene compounds and 4-brominated substituted indene compounds can be used to produce corresponding coupling products by known methods such as the Suzuki-Miyaura coupling reaction using a palladium catalyst as shown below, and the production method is not particularly limited.

[0108] [ka]

[0109] As in the above, there are positional isomers of the double bond of the five-membered ring portion of the indene compound, and a mixture of these isomers may be used. Instead of boronic acid, other boron compounds such as various boronic acid esters or boroxines may be used, the reaction mixture of a halogen compound and a metal reagent followed by a boron compound may be used without isolation and purification, and a nickel catalyst or an iron catalyst may be used instead of a palladium catalyst. In addition to the above-mentioned known production methods, for example, JP 2014-196274 A may be mentioned.

[0110] In addition, instead of the Suzuki-Miyaura coupling reaction using a boron compound, the coupling product may be produced by the Negishi coupling reaction with an organozinc reagent, the Mizoroki-Heck reaction with an alkene compound, the Hiyama coupling reaction with an organosilicon compound, the Sonogashira-Hagiwara coupling reaction with a terminal alkyne compound, the Migita-Kosugi-Stille coupling reaction with an organotin compound, the Kumada-Tamao-Corriu coupling reaction with an organomagnesium compound, the Buchwald-Hartwig coupling reaction, the Goldberg amination reaction, or the Ullmann ether synthesis reaction. Examples of known production methods include those described above, as well as those disclosed in JP-A-8-183814, JP-T-2005-529865, and JP-T-2006-509046.

[0111] The coupling product may be produced by a known method such as a direct coupling reaction using the 2-unsubstituted indene compound and an aromatic halide in the presence of a palladium catalyst.

[0112] [ka]

[0113] In the formula (3), Ar represents an aromatic substituent, and a mixture of positional isomers of the double bond at the five-membered ring portion of the indene compound may be used. Known production methods include those described in JP-A-2000-512661 and JP-A-2014-201519. The transition metal compound (A) and the precursor compound (ligand) can be produced by known methods using various substituted indene compounds produced by the above-mentioned methods, etc. When Q is a silicon atom, a germanium atom, or a tin atom, they can be produced by the following methods, and the production method is not particularly limited.

[0114] [ka]

[0115] In the synthesis of the precursor compound (ligand) in [Formula 4], the organomagnesium reagent prepared from the 2-brominated substituted indene compound and the organolithium reagent prepared from the substituted 1-indene compound are preferably reacted with a chloride containing Q in a stepwise manner, in any order. After the reaction with the organometallic reagent in the first step, by-product inorganic compounds may be removed under an inert atmosphere, or the reaction product may be isolated by distillation, crystallization, washing, or other procedures before use. In the reaction with the organometallic reagent in the second step, DMI (1,3-dimethyl-2-imidazolidinone), DMPU (N,N'-dimethylpropyleneurea), HMPA (hexamethylphosphoric triamide), or the like is preferably added in an amount of 0.1 to 5.0 equivalents relative to the organometallic reagent, with 1.0 equivalent of DMI being more preferred. The substituted indene compound and the precursor compound (ligand) contain positional isomers of the double bond in the five-membered ring portion of the indene compound, and a mixture of these isomers may also be used.

[0116] In addition to the above-mentioned known methods for producing the transition metal compound (A) and the precursor compound (ligand), methods such as those described in JP-A-11-315089, JP-A-2001-302687, JP-A-2001-220404, "Collection of Polymers 2002, 59, 243," JP-A-2003-522194, "Macromolecules 2004, 37, 2342," JP-A-2007-320935, and JP-A-2011-126813 can be cited.

[0117] When Q is a carbon atom, the compound can be produced by the following method, but the production method is not particularly limited.

[0118] [ka]

[0119] In Formula 5, base is a basic substance capable of generating an indenyl anion, and examples thereof include, but are not limited to, 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. In the presence of a basic substance, a fulvene compound can be synthesized from a substituted 1-indene compound and a carbonyl compound by a known method. A precursor compound (ligand) can be produced by reacting the fulvene compound with an organomagnesium reagent prepared from a 2-brominated substituted indene compound. The substituted indene compound and the precursor compound (ligand) contain positional isomers of the double bond at the five-membered ring portion of the indene compound, and a mixture of these isomers may also be used.

[0120] In addition to the above-mentioned known methods for producing the transition metal compound (A) and the precursor compound (ligand), there are also known methods described in "Macromolecules 2003, 36, 9325," "Organometallics 2004, 23, 5332," "Eur. J. Inorg. Chem. 2005, 1003," and "Eur. J. Inorg. Chem. 2009, 1759."

[0121] [Solid Carrier (C)] The present olefin polymerization catalyst contains a solid support (C). The solid carrier (C) may be used singly or in combination of two or more.

[0122] The solid carrier (C) is an inorganic compound, and is a granular or fine particle solid. The inorganic compound is preferably a porous oxide, an inorganic halide, clay, a clay mineral, or an ion-exchangeable layered compound, and more preferably a porous oxide.

[0123] Specific examples of the porous oxide that can be used include SiO2, Al2O3, MgO, ZrO, TiO2, BO3, CaO, ZnO, BaO, ThO2, etc., and composites or mixtures containing these, as well as natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-VO5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc. Of these, porous oxides containing SiO2 and / or Al2O3 as the main component are preferred.

[0124] The porous oxide may contain small amounts of carbonates, sulfates, nitrates, and oxides such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, and Li2O.

[0125] The properties of the porous oxide vary depending on the type and manufacturing method, but the particle size is preferably 10 to 300 μm, more preferably 20 to 200 μm, and the specific surface area is preferably 50 to 1,000 m. 2 / g, more preferably 100 to 700m 2 / g, and the pore volume is preferably 0.3 to 3.0 cm 3 / g range. Such porous oxides are preferably fired at 100 to 1,000°C, more preferably 150 to 700°C, as required, before use.

[0126] Examples of inorganic halides that can be used include MgCl, MgBr, MnCl, and MnBr. The inorganic halides may be used as they are or may be pulverized using a ball mill or a vibration mill. Alternatively, the inorganic halides may be dissolved in a solvent such as alcohol and then precipitated into fine particles using a precipitating agent.

[0127] The clay is usually composed mainly of clay minerals. The ion-exchangeable layered compounds are compounds having a crystalline structure in which planes formed by ionic bonds or the like are stacked parallel to one another with weak bonding forces, and the ions they contain are exchangeable. Most clay minerals are ion-exchangeable layered compounds. These clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products, and synthetic compounds can also be used.

[0128] Examples of clay, clay minerals, or ion-exchange layered compounds include ionic crystalline compounds having layered crystal structures such as hexagonal close packing type, antimony type, CdCl2 type, and CdI2 type.

[0129] Furthermore, examples of clay and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, halloysite, etc. Ion-exchangeable layered compounds include crystalline acid 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.

[0130] Such clays, clay minerals, or ion-exchangeable layered compounds preferably have a pore volume of 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g, having a radius of 20 Å or more, as measured by mercury intrusion porosimetry. Here, the pore volume is measured by mercury intrusion porosimetry using a mercury porosimeter for pores with a radius of 20 to 30,000 Å. When a carrier having a pore volume of less than 0.1 cc / g with a radius of 20 Å or more is used, it tends to be difficult to obtain high polymerization activity.

[0131] It is also preferable to subject the clay and clay minerals to chemical treatment. Chemical treatments include surface treatments that remove impurities from 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 not only removes surface impurities but also increases the surface area by eluting cations such as Al, Fe, and Mg in the crystalline structure. Alkali treatment destroys the crystalline structure of the clay, resulting in structural changes. Furthermore, salt treatment and organic treatment form ionic complexes, molecular complexes, organic derivatives, and the like, which can change the surface area and interlayer distance.

[0132] The ion-exchangeable layered compound may be a layered compound in which the interlayer spacing is expanded by utilizing the ion exchange property and exchanging the exchangeable ions between the layers with other large, bulky ions. Such bulky ions act as supports supporting 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 to be intercalated 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 +, [Zr(OH) 14 ] 2+, and metal hydroxide ions such as [Fe3O(OCOCH3)6]+. These compounds may be used alone or in combination of two or more.

[0133] Furthermore, when intercalating these compounds, polymers obtained by hydrolysis of metal alkoxides (R represents a hydrocarbon group, etc.) such as Si(OR)4, Al(OR)3, and Ge(OR)4, and colloidal inorganic compounds such as SiO2, can also be present. Examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them with heat.

[0134] The clay, clay mineral, and ion-exchangeable layered compound may be used as received, or may be used after treatment such as ball milling or sieving. They may also be used after adding and adsorbing fresh water or after heat dehydration. Furthermore, they may be used alone or in combination of two or more.

[0135] Of these, clay or clay minerals are preferred, and montmorillonite, vermiculite, pectolite, taeniolite and synthetic mica are particularly preferred.

[0136] [Compound (B)] The present olefin polymerization catalyst further comprises, in addition to the components (A) and (C), The composition contains at least one compound (B) (hereinafter also referred to as "component (B)") selected from the group consisting of an organometallic compound (B-1) (hereinafter also referred to as "component (B-1)") represented by the following general formula (B-1a), (B-1b), or (B-1c), an organoaluminum oxy compound (B-2) (hereinafter also referred to as "component (B-2)"), and a compound (B-3) (hereinafter also referred to as "component (B-3)") that reacts with a transition metal compound (A) to form an ion pair.

[0137] R a m Al(OR b ) n Hp X q …(B-1a) 〔In general formula (B-1a), R a and R b each represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other; X represents a halogen atom; m is a number such that 0 < m ≤ 3, n is a number such that 0 ≤ n < 3, p is a number such that 0 ≤ p < 3, q is a number such that 0 ≤ q < 3, and m + n + p + q = 3.〕

[0138] M a AlR a 4…(B-1b) 〔In general formula (B-1b), M a represents Li, Na or K; and R a represents a hydrocarbon group having 1 to 15 carbon atoms.〕

[0139] R a r M b R b s X t …(B-1c) 〔In general formula (B-1c), R a and R b each represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same or different from each other; M b is selected from Mg, Zn and Cd; X represents a halogen atom; r is a number such that 0 < r ≤ 2, s is a number such that 0 ≤ s ≤ 1, t is a number such that 0 ≤ t ≤ 1, and r + s + t = 2.〕

[0140] As the component (B-1), the compounds disclosed in Japanese Patent Application Laid-Open No. 11-315109 by the present applicant and in EP0874005A can be used without limitation. The component (B-1) is preferably one represented by the general formula (B-1a), and specific examples thereof include trialkylaluminums 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 of the aluminum dihalide include alkyl aluminum dihalides such as isopropyl aluminum dichloride and ethyl aluminum dibromide; alkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, dihydrophenyl aluminum hydride, diisopropyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, diisohexyl aluminum hydride, diphenyl aluminum hydride, dicyclohexyl aluminum hydride, di-sec-heptyl aluminum hydride and di-sec-nonyl aluminum hydride; and dialkyl aluminum alkoxides such as dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisopropyl aluminum methoxide and diisobutyl aluminum ethoxide. The component (B-1) may be used singly or in combination of two or more.

[0141] As the component (B-2), aluminoxanes prepared from trialkylaluminum or tricycloalkylaluminum are preferred, and organoaluminum oxy compounds prepared from trimethylaluminum or triisobutylaluminum are particularly preferred. The component (B-2) may be used singly or in combination of two or more.

[0142] As the component (B-3) that reacts with the transition metal compound (A) to form an ion pair, Lewis acids, ionic compounds, borane compounds, and carborane compounds, as well as heteropoly compounds and isopoly compounds, described in, for example, JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and U.S. Pat. No. 5,321,106, can be used without limitation. The component (B-3) may be used singly or in combination of two or more.

[0143] In the present olefin polymerization catalyst, when component (B-2) such as methylaluminoxane is used in combination as a co-catalyst component, not only does it exhibit extremely high catalytic activity toward ethylene, but it also makes it possible to easily prepare a solid support component containing the co-catalyst component by reacting with active hydrogen in the solid support, and therefore it is preferred to use component (B-2) as component (B).

[0144] <Instructions and order of addition of each ingredient> The method for producing an olefin polymerization catalyst of the present invention comprises a step of mixing and contacting component (A), component (C), and component (B) in an inert hydrocarbon solvent, and is characterized in that component (A) is contacted with component (C) at a temperature below 20°C.

[0145] As a method for contacting each component, when paying attention to the order of contact, for example, (i) A method in which component (C) is contacted with component (B) and then with component (A). (ii) A method in which component (A) is mixed with component (B) and then contacted with component (C). (iii) A method of contacting component (C) with component (B) and then contacting a mixture of component (A) and component (B) with component (C) (iv) A method of contacting component (C) with component (B), further contacting with component (B), and then contacting with a mixture of component (A) and component (B). When multiple types of component (B) are used, the components (B) may be the same or different. Of the above methods, method (i) is preferred. As will be described later, when preparing a prepolymerization catalyst component, component (B) may be further added, if necessary, after the contact in methods (i) to (iv).

[0146] The present invention is characterized in that component (A) and component (C) are contacted at a temperature of less than 20°C. Therefore, in methods (i), (iii), and (iv), the temperature is less than 20°C when component (A) (or a mixture of components (A) and (B)) is contacted with the contact product of components (C) and (B), and in method (ii), the temperature is less than 20°C when component (C) is contacted with the mixture of components (A) and (B).

[0147] In each of the processes showing the above contacting order forms, in the step including the contact of component (C), by allowing the coexistence of component (D) below, fouling during the polymerization reaction can be suppressed and the particle properties of the resulting polymer can be improved. As component (D), a compound having a polar functional group can be used, and a nonionic surfactant is preferred, with polyalkylene oxide block, higher aliphatic amide, polyalkylene oxide, polyalkylene oxide alkyl ether, alkyldiethanolamine, polyoxyalkylene alkylamine, glycerin fatty acid ester, and N-acylamino acid being more preferred. These may be used alone or in combination of two or more.

[0148] The solvent used in preparing the present olefin polymerization catalyst includes an inert hydrocarbon solvent, and specific examples thereof 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; and mixtures thereof.

[0149] In the contact of component (B) with component (C) in methods (i), (iii), and (iv), a reactive site in component (B) reacts with a reactive site in component (C) to chemically bond them, forming a contact product of component (B) and component (C). The contact time of component (B) with component (C) is usually 1 minute to 20 hours, preferably 30 minutes to 10 hours, and more preferably 30 minutes to 4 hours, and the contact temperature is usually -50 to 200°C, preferably -20 to 120°C, and more preferably 0 to 100°C.

[0150] If the initial contact between component (B) and component (C) is carried out too quickly, the heat generated by the reaction or the reaction energy will cause component (C) to collapse, deteriorating the morphology of the resulting solid catalyst component, and when this is used in polymerization, poor polymer morphology often makes continuous operation difficult. Therefore, it is preferable to initially contact component (B) and component (C) at a lower temperature in order to suppress the heat generated by the reaction, or to control the heat generated by the reaction and react at a rate that allows the initial contact temperature to be maintained.

[0151] When component (B) is contacted with component (C) and then further contacted with component (B), the contact time between the contact product of component (B) and component (C) and further component (B) is usually 0.5 minutes to 4 hours, preferably 1 minute to 2 hours, and more preferably 2 minutes to 1 hour, and the contact temperature is usually −50 to 200°C, preferably −20 to 120°C, and more preferably 0 to 100°C.

[0152] The contact mass ratio between component (B) and component (C) (mass of component (B) / mass of component (C)) can be selected arbitrarily, but a higher contact mass ratio allows a larger amount of component (A) to be brought into contact with the mixture of component (B) and component (C), thereby improving the catalytic activity per mass of the solid catalyst component. The contact mass ratio of component (B) to component (C) (mass of component (B) / mass of component (C)) is preferably 0.05 to 3.0, more preferably 0.1 to 2.0.

[0153] In methods (i), (iii), and (iv), when the contact product of component (B) and component (C) is contacted with component (A) (or a mixture of components (A) and (B)), or in method (ii), when the mixture of components (A) and (B) is contacted with component (C), the contact time is preferably 1 minute to 20 hours, more preferably 3 minutes to 10 hours, even more preferably 5 minutes to 3 hours, and particularly preferably 10 minutes to 2 hours, and the contact temperature is less than 20°C, preferably -78 to 15°C, more preferably -60°C to 10°C, even more preferably -50°C to 5°C, and particularly preferably -40°C to 3°C.

[0154] Component (B-1) is used in an amount such that the molar ratio of component (B-1) to the total transition metal atoms (M) in component (A) [(B-1) / M] is generally 0.01 to 100,000, preferably 0.05 to 50,000, more preferably 1.0 to 5,000, even more preferably 10 to 1,000, and particularly preferably 20 to 100.

[0155] Component (B-2) is used in an amount such 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 generally 10 to 500,000, preferably 20 to 100,000, more preferably 30 to 10,000, even more preferably 40 to 1,000, and particularly preferably 50 to 500.

[0156] Component (B-3) is used in an amount such that the molar ratio of component (B-3) to the total transition metal atoms (M) in component (A) [(B-3) / M] is generally 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 analysis).

[0157] For ethylene polymerization, the present olefin polymerization catalyst can be used as it is, but it can also be used after prepolymerizing an olefin on the present olefin polymerization catalyst to form a prepolymerized catalyst component.

[0158] The prepolymerized catalyst component can be prepared by prepolymerizing ethylene or the like in the presence of the present olefin polymerization catalyst, usually in an inert hydrocarbon solvent, and can be carried out in any of a batch system, a semi-continuous system, or a continuous system, and can be carried out under reduced pressure, normal pressure, or increased pressure. Furthermore, it is desirable that the prepolymerized catalyst component be produced by the prepolymerization in an amount of usually 0.01 to 1,000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g, and particularly preferably 1.0 to 5.0 g, per 1 g of the solid catalyst component.

[0159] The prepolymerized catalyst component produced in the inert hydrocarbon solvent may be separated from the suspension and then resuspended in the inert hydrocarbon solvent, and ethylene may be introduced into the resulting suspension. Alternatively, the suspension may be dried and then ethylene may be introduced.

[0160] The prepolymerization temperature is usually -20 to 80°C, preferably 0 to 60°C, more preferably 10 to 50°C, and still more preferably 15 to 40°C, and the prepolymerization time is usually 0.5 to 100 hours, preferably 1 to 50 hours, more preferably 2 to 20 hours, and still more preferably 3 to 10 hours. For the prepolymerization, an olefin containing ethylene as a main component is preferably used.

[0161] The form of the solid catalyst component used in the prepolymerization can be any of those already mentioned without any limitations. If necessary, component (B) is used, and an organoaluminum compound (B-1a) is particularly preferred. When component (B) is used, component (B) is used in an amount such that the molar ratio (Al / M) of the aluminum atom (Al) in component (B) to the transition metal atom (M) in the transition metal compound (A) is generally 0.1 to 10,000, preferably 0.5 to 5,000, more preferably 30 to 1,000, even more preferably 40 to 500, and particularly preferably 100 to 500.

[0162] The concentration of the olefin polymerization catalyst in the prepolymerization system is usually 1 to 1,000 g / L, preferably 10 to 500 g / L, in terms of ethylene polymerization catalyst / polymerization volume ratio. During the prepolymerization, the above-mentioned component (D) may be present in order to suppress fouling or improve particle properties.

[0163] Furthermore, for the purpose of improving the fluidity of the prepolymerized catalyst component and suppressing the occurrence of heat spots, sheeting, and polymer lumps during polymerization, component (D) may be brought into contact with a prepolymerized solid catalyst component once produced by prepolymerization.

[0164] The temperature when contacting the component (D) 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 the present olefin polymerization catalyst is contacted with component (D), component (D) is usually used in an amount of 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass, more preferably 0.4 to 5 parts by mass, and even more preferably 0.8 to 2 parts by mass, per 100 parts by mass of the present olefin polymerization catalyst.

[0165] The olefin polymerization catalyst and component (D) can be mixed and contacted in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include those similar to those mentioned above. In the method for producing an ethylene polymer according to the present invention, a dried prepolymerized catalyst component (hereinafter also referred to as a "dried prepolymerized catalyst") can be used as the olefin polymerization catalyst. Drying of the prepolymerized catalyst component is usually carried out after removing the hydrocarbon dispersant from the obtained suspension of the prepolymerized catalyst by filtration or the like.

[0166] The prepolymerized solid catalyst component is dried by maintaining the prepolymerized solid catalyst component under a flow of inert gas, usually at a temperature of 70°C or less, preferably in the range of 20 to 50°C. The amount of volatile components in the obtained dried prepolymerized catalyst is usually 2.0% by mass or less, preferably 1.0% by mass or less. The amount of volatile components in the dried prepolymerized catalyst is better as it is lower, and there is no particular lower limit, but practically 0.001% by mass is preferred. The drying time is usually 1 to 48 hours, depending on the drying temperature.

[0167] The dry prepolymerized catalyst has excellent fluidity and can be stably supplied to a polymerization reactor. Furthermore, the use of the dry prepolymerized catalyst makes it possible to carry out stable polymerization because the solvent used for suspension does not need to be entrained in the gas-phase polymerization system.

[0168] [Method of producing ethylene polymer] The process for producing an ethylene polymer of the present invention is characterized by polymerizing ethylene or polymerizing ethylene and an olefin having from 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst of the present invention.

[0169] In the present invention, the ethylene content in the ethylene polymer is preferably 70 mol % or more (the total of the monomer units is taken as 100 mol %). Examples of the polymerization method include liquid phase polymerization methods such as solution polymerization and suspension polymerization, and gas phase polymerization methods, with suspension polymerization methods and gas phase polymerization methods being preferred.

[0170] Specific examples of the inert hydrocarbon solvent used in the liquid phase polymerization method 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; and mixtures thereof.

[0171] When ethylene is polymerized using the present olefin polymerization catalyst, component (A) is usually used in an amount of 1 x 10 per 1 L of reaction volume. -12 ~1×10 -1 mol, preferably 1 x 10 -8 ~1×10 -2 It is preferably used in an amount so as to obtain a molar ratio of 1:1. Also, component (B) is preferably used, and more preferably Preferably, a compound represented by the general formula (B-1a) or component (B-2) is used.

[0172] When polymerizing ethylene, the polymerization temperature is preferably 0°C or higher, more preferably 40°C or higher, and even more preferably 60°C or higher. A higher temperature is advantageous in terms of heat removal and the like in industrial-scale production. The upper limit of the polymerization temperature is usually 200°C, preferably 170°C, and the polymerization pressure is usually normal pressure to 100 kgf / cm. 2 (10 MPaG (gauge pressure)), preferably normal pressure to 50 kgf / cm 2 (5MPaG), more preferably normal pressure to 20kgf / cm 2 (2MPaG).

[0173] The polymerization reaction can be carried out in any of batch, semi-continuous and continuous systems, and can also be carried out in two or more stages with different reaction conditions. The molecular weight of the ethylene polymer obtained by the method for producing an ethylene polymer according to the present invention can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature. During the polymerization, the component (D) can be added to the polymerization system in order to suppress fouling or improve particle properties.

[0174] In the present invention, the monomer supplied to the polymerization reaction is ethylene alone, or ethylene and an olefin having from 3 to 20 carbon atoms. Specific examples of the olefin having from 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, and 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.

[0175] Furthermore, small amounts of styrene, vinylcyclohexane, dienes, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, and polar monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid may be supplied within a range that does not impair the effects of the present invention.

[0176] According to the method for producing an ethylene polymer of the present invention, an ethylene polymer having a high bulk density can be produced. The present inventors believe that the mechanism by which the bulk density of the resulting ethylene polymer is increased is that by contacting component (A) with component (C) at a low temperature (for example, below 20°C), component (A) is evenly distributed on component (C), and a polymer grows uniformly from the surface of component (C), thereby enabling the production of an ethylene polymer having a higher bulk density.

[0177] [Ethylene polymer] The ethylene polymer produced by the method for producing an ethylene polymer according to the present invention (hereinafter also referred to as the "present ethylene polymer") preferably has a bulk density of 0.39 g / cm. 3 or more, more preferably 0.39 to 0.45 g / cm 3 , and more preferably 0.39 to 0.44 g / cm 3 , particularly preferably 0.40 to 0.43 g / cm 3 is. The bulk density of the present ethylene polymer is measured according to the method described in the examples below. When the bulk density of the ethylene polymer is within the above range, fouling during the production of the ethylene polymer and clogging of the transfer pipes can be suppressed, and the operability in gas phase polymerization can be improved.

[0178] The ethylene polymer may be pelletized. The ethylene polymer may be blended with additives such as weather resistance stabilizers, heat resistance stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, nucleating agents, plasticizers, antioxidants, hydrochloric acid absorbers, and antioxidants, as needed, within the scope of the invention.

[0179] The present ethylene polymer can be processed by ordinary film molding, blow molding, injection molding and extrusion molding. Examples of molded articles obtained by processing the present ethylene polymer include films, blown infusion bags, blown bottles, gasoline tanks, extrusion-molded tubes, pipes, tear-off caps, injection-molded articles such as daily commodities, fibers, and large-sized rotational molded articles.

[0180] Films obtained by processing the present ethylene polymer are suitable for various packaging films such as packaging bags for liquids, liquid soup pouches, liquid paper containers, laminated raw material, special-shaped liquid packaging bags (standing pouches, etc.), standard bags, heavy-duty bags, cling film, sugar bags, oily food packaging bags, food packaging films, protective films, infusion bags, agricultural materials, etc., and can also be used as multilayer films by bonding with a substrate such as nylon or polyester. [Example]

[0181] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. [Measurement of various physical properties] The methods for measuring the physical properties of the ethylene polymer are shown below. <Bulk density> The bulk density of the ethylene polymer was measured according to the following method. Approximately 120 mL of sample was placed in a funnel inserted into the damper of a bulk density measuring device conforming to JIS K 6720 (bulk density measuring device for vinyl chloride resin, manufactured by Ito Seisakusho Co., Ltd.), and then the damper was quickly removed and the sample was dropped into a receiver. After scraping off the sample that had risen from the receiver, the mass of the receiver containing the sample was weighed and the bulk density was calculated using the following formula. The measurement was carried out three times, and the average value was used as the bulk density (g / mL = g / cm) of the ethylene polymer. 3 ) was decided. Sa=(CA) / B (Sa is the bulk density (g / mL), A is the mass of the receiver (g), B is the internal volume of the receiver (mL), and C is the mass of the receiver containing the sample (g).)

[0182] The transition metal compounds (A) used in the examples are as follows: Transition metal compound (A): dimethylsilylene(2-indenyl)(4-(3,5-di-tert-butyl-4-methoxyphenyl)-7-methoxy-1-indenyl)zirconium dichloride [compound represented by the following formula (synthesized by the method described in Synthesis Example 8-4 of JP 2019-059933 A)]

[0183] [ka]

[0184] [Example 1-1] <Preparation of Carrier Component (Contacting Component (B) with Component (C))> A 270 L reactor equipped with a stirrer was charged with silica gel (Fuji Silysia Co., Ltd.: average particle size 70 μm, specific surface area 340 m) as a solid carrier (C) under a nitrogen atmosphere. 2 / g, pore volume 1.3cm 3 10 kg of the compound (B) (3.5 mol / L in terms of Al atoms) was suspended in 77 L of toluene and then cooled to 0-5°C. 20.4 L of a toluene solution of methylaluminoxane (compound (B)) (3.5 mol / L in terms of Al atoms) was added dropwise to this suspension over 30 minutes. The temperature in the system was maintained at 0-5°C. After the reaction was continued at 0-5°C for 30 minutes, the temperature was raised to 95-100°C over approximately 1.5 hours and then continued at 95-100°C for 4 hours. The temperature was then lowered to room temperature, the supernatant liquid was removed by decantation, and the mixture was washed twice with toluene to prepare a toluene slurry with a total volume of 58.0 L. A portion of the resulting slurry components was sampled and its concentration was examined. The slurry concentration was 198.0 g / L, and the Al concentration was 0.97 mol / L.

[0185] <Preparation of Prepolymerization Catalyst (X-1)> A 200 mL reactor equipped with a stirrer and thoroughly purged with nitrogen was charged with 9.1 mL of the toluene slurry of the carrier components (B) / (C) obtained above and 23.6 mL of toluene, and 7.3 mL of a 6 mM toluene solution of the transition metal compound (A) was added. The mixture was allowed to come into contact with the carrier components (B) / (C) at a system temperature of 2.5°C for 1 hour, after which the supernatant liquid was removed by decantation and the mixture was washed twice with hexane to prepare a slurry with a total volume of 39.0 mL. The resulting slurry was adjusted to 10-15°C, and 1.7 mL of a 0.93 M hexane solution of diisobutylaluminum hydride was added. After 10 minutes of stirring, ethylene gas supply was initiated, and 0.03 mL of 1-hexene was added. The system temperature was raised to 25°C, and 0.03 mL of 1-hexene was added 1 hour 30 minutes and 3 hours after the start of ethylene gas supply. The system temperature was raised again to 35°C, and 0.03 mL of 1-hexene was added 4 hours 30 minutes after the start of ethylene gas supply. The ethylene supply was stopped 6 hours after the start of ethylene gas supply. Next, the system was thoroughly purged with nitrogen, the supernatant was removed by decantation, and the mixture was washed four times with hexane to prepare a total volume of 40.0 mL of slurry. To the obtained slurry, 9.2 mL of an 8 mg / mL hexane solution of Electrostripper EA (manufactured by Kao Corporation) was added, and the mixture was allowed to come into contact for 2 hours while maintaining the temperature in the system at 37.5° C. Next, the hexane slurry was transferred to a glass Schlenk flask with an internal volume of 100 mL, and the hexane was distilled off under reduced pressure at 25° C. for 1 hour, thereby obtaining 7.1 g of a prepolymerization catalyst (X-1).

[0186] [Example 1-2] <Preparation of Prepolymerization Catalyst (X-2)> A 200 mL reactor equipped with a stirrer and thoroughly purged with nitrogen was charged with 9.1 mL of the toluene slurry of the carrier components (B) / (C) obtained in Example 1-1 above and 23.6 mL of toluene, and 7.3 mL of a 6 mM toluene solution of the transition metal compound (A) was added. The mixture was allowed to come into contact with the carrier components (B) / (C) at a system temperature of −20° C. for 1 hour, after which the supernatant liquid was removed by decantation and the mixture was washed twice with hexane to prepare a slurry with a total volume of 39.0 mL. The resulting slurry was adjusted to 10-15°C, and 1.7 mL of a 0.93 M hexane solution of diisobutylaluminum hydride was added. After 10 minutes of stirring, ethylene gas supply was initiated, and 0.03 mL of 1-hexene was added. The system temperature was raised to 25°C, and 0.03 mL of 1-hexene was added 1 hour 30 minutes and 3 hours after the start of ethylene gas supply. The system temperature was raised again to 35°C, and 0.03 mL of 1-hexene was added 4 hours 30 minutes after the start of ethylene gas supply. The ethylene supply was stopped 6 hours after the start of ethylene gas supply. Next, the system was thoroughly purged with nitrogen, the supernatant was removed by decantation, and the mixture was washed four times with hexane to prepare a total volume of 40.0 mL of slurry. To the obtained slurry, 9.2 mL of an 8 mg / mL hexane solution of Electrostripper EA (manufactured by Kao Corporation) was added, and the mixture was allowed to come into contact for 2 hours while maintaining the temperature in the system at 37.5° C. Next, the above hexane slurry was transferred to a glass Schlenk flask with an internal volume of 100 mL, and the hexane was distilled off under reduced pressure at 25° C. for 1 hour, thereby obtaining 7.1 g of a prepolymerization catalyst (X-2).

[0187] [Comparative Example 1-1] <Preparation of Prepolymerization Catalyst (X-3)> A 200 mL reactor equipped with a stirrer and thoroughly purged with nitrogen was charged with 9.1 mL of the toluene slurry of the carrier components (B) / (C) obtained in Example 1-1 above and 23.6 mL of toluene, and 7.3 mL of a 6 mM toluene solution of the transition metal compound (A) was added. The mixture was allowed to come into contact with the carrier components (B) / (C) at a system temperature of 22.5°C for 1 hour, after which the supernatant liquid was removed by decantation and the mixture was washed twice with hexane to prepare a slurry with a total volume of 39.0 mL. The resulting slurry was adjusted to 10-15°C, and 1.7 mL of a 0.93 M hexane solution of diisobutylaluminum hydride was added. After 10 minutes of stirring, ethylene gas supply was initiated, and 0.03 mL of 1-hexene was added. The system temperature was raised to 25°C, and 0.03 mL of 1-hexene was added 1 hour 30 minutes and 3 hours after the start of ethylene gas supply. The system temperature was raised again to 35°C, and 0.03 mL of 1-hexene was added 4 hours 30 minutes after the start of ethylene gas supply. The ethylene supply was stopped 6 hours after the start of ethylene gas supply. Next, the system was thoroughly purged with nitrogen, the supernatant was removed by decantation, and the mixture was washed four times with hexane to prepare a total volume of 40.0 mL of slurry. To the obtained slurry, 9.2 mL of an 8 mg / mL hexane solution of Electrostripper EA (manufactured by Kao Corporation) was added, and the mixture was contacted for 2 hours while maintaining the temperature in the system at 37.5° C. Next, the above hexane slurry was transferred to a glass Schlenk flask with an internal volume of 100 mL, and the hexane was distilled off under reduced pressure at 25° C. for 1 hour, thereby obtaining 7.0 g of prepolymerization catalyst (X-3).

[0188] [Comparative Example 1-2] <Preparation of Prepolymerized Catalyst (X-4)> A 200 mL reactor equipped with a stirrer and thoroughly purged with nitrogen was charged with 9.1 mL of the toluene slurry of the carrier components (B) / (C) obtained in Example 1-1 above and 25.0 mL of toluene, and 5.9 mL of a 6 mM toluene solution of the transition metal compound (A) was added. The mixture was contacted at a system temperature of 40°C for 1 hour, after which the supernatant liquid was removed by decantation and the mixture was washed twice with hexane to prepare a slurry with a total volume of 37.2 mL. The resulting slurry was adjusted to 10-15°C, and 3.5 mL of a 0.93 M hexane solution of diisobutylaluminum hydride was added. After 10 minutes of stirring, ethylene gas supply was initiated, and 0.12 mL of 1-hexene was added. The system temperature was raised to 25°C, and 0.12 mL of 1-hexene was added 1 hour 30 minutes and 3 hours after the start of ethylene gas supply. The system temperature was again raised to 32-38°C, and 0.12 mL of 1-hexene was added 4 hours 30 minutes after the start of ethylene gas supply. The ethylene supply was stopped 6 hours after the start of ethylene gas supply. Next, the system was thoroughly purged with nitrogen, the supernatant was removed by decantation, and the mixture was washed four times with hexane to prepare a total volume of 40.0 mL of slurry. To the obtained slurry, 0.91 mL of a 50 mg / mL hexane solution of Emulgen 108 (manufactured by Kao Corporation) was added, and the mixture was contacted for 2 hours while maintaining the temperature in the system at 37.5° C. Next, the above hexane slurry was transferred to a glass Schlenk flask with an internal volume of 100 mL, and the hexane was distilled off under reduced pressure at 25° C. for 1 hour, thereby obtaining 7.0 g of a prepolymerization catalyst (X-4).

[0189] [Comparative Example 1-3] <Preparation of Prepolymerization Catalyst (X-5)> A 200 mL reactor equipped with a stirrer and thoroughly purged with nitrogen was charged with 9.1 mL of the toluene slurry of the carrier components (B) / (C) obtained in Example 1-1 above and 25.0 mL of toluene, and 5.9 mL of a 6 mM toluene solution of the transition metal compound (A) was added. The mixture was allowed to come into contact with the carrier components (B) / (C) at a system temperature of 60°C for 1 hour. The supernatant was then removed by decantation, and the mixture was washed twice with hexane to prepare a slurry with a total volume of 37.2 mL. The resulting slurry was adjusted to 10-15°C, and 3.5 mL of a 0.93 M hexane solution of diisobutylaluminum hydride was added. After 10 minutes of stirring, ethylene gas supply was initiated, and 0.12 mL of 1-hexene was added. The system temperature was raised to 25°C, and 0.12 mL of 1-hexene was added 1 hour 30 minutes and 3 hours after the start of ethylene gas supply. The system temperature was again raised to 32-38°C, and 0.12 mL of 1-hexene was added 4 hours 30 minutes after the start of ethylene gas supply. The ethylene supply was stopped 6 hours after the start of ethylene gas supply. Next, the system was thoroughly purged with nitrogen, the supernatant was removed by decantation, and the mixture was washed four times with hexane to prepare a total volume of 40.0 mL of slurry. To the obtained slurry, 0.91 mL of a 50 mg / mL hexane solution of Emulgen 108 (manufactured by Kao Corporation) was added, and the mixture was contacted for 2 hours while maintaining the temperature in the system at 37.5° C. Next, the above hexane slurry was transferred to a glass Schlenk flask with an internal volume of 100 mL, and the hexane was distilled off under reduced pressure at 25° C. for 1 hour, thereby obtaining 6.9 g of a prepolymerization catalyst (X-5).

[0190] [Example 2-1] 500 mL of heptane was added to a 1 L stainless steel autoclave equipped with a stirring blade, which had been thoroughly purged with nitrogen, under a nitrogen atmosphere. Then, ethylene was passed through the autoclave to saturate the liquid and gas phases with ethylene. Next, 3 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 0.20 g of prepolymerization catalyst (X-1) powder were charged, and the mixture was heated at 80°C and 0.8 MPaG (8.16 kgf / cm) using ethylene gas. 2 The temperature and pressure were raised to 80°C, and the polymerization reaction was carried out for 90 minutes. The obtained polymer was filtered and then vacuum dried at 80°C for 10 hours to obtain an ethylene-1-hexene copolymer. The bulk density of the obtained ethylene-1-hexene copolymer was 0.40 g / cm. 3 It was.

[0191] [Example 2-2] An ethylene-1-hexene copolymer was obtained in the same manner as in Example 2-1, except that the prepolymerization catalyst (X-2) was used instead of the prepolymerization catalyst (X-1). The bulk density of the obtained ethylene-1-hexene copolymer was 0.40 g / cm. 3 It was.

[0192] [Comparative Example 2-1] An ethylene-1-hexene copolymer was obtained in the same manner as in Example 2-1, except that the prepolymerization catalyst (X-3) was used instead of the prepolymerization catalyst (X-1). The bulk density of the obtained ethylene-1-hexene copolymer was 0.38 g / cm. 3 It was.

[0193] [Comparative Example 2-2] An ethylene-1-hexene copolymer was obtained in the same manner as in Example 2-1, except that the prepolymerized catalyst (X-4) was used instead of the prepolymerized catalyst (X-1). The bulk density of the obtained ethylene-1-hexene copolymer was 0.34 g / cm. 3 It was.

[0194] [Comparative Example 2-3] An ethylene-1-hexene copolymer was obtained in the same manner as in Example 2-1, except that the prepolymerized catalyst (X-5) was used instead of the prepolymerized catalyst (X-1). The bulk density of the obtained ethylene-1-hexene copolymer was 0.34 g / cm. 3 It was.

[0195] When prepolymerization catalyst (X-1) obtained by contacting component (A) with component (C) at 2.5°C or prepolymerization catalyst (X-2) obtained by contacting component (A) with component (C) at -20°C was used (Example 2-1 and Example 2-2, respectively), ethylene-1-hexene copolymers with higher bulk densities were obtained compared to when prepolymerization catalysts (X-3) to (X-5) obtained by contacting component (A) with component (C) at 22.5°C, 40°C, or 60°C were used (Comparative Examples 2-1 to 2-3).

Claims

1. A transition metal compound (A) represented by the following general formula [1], at least one compound (B) selected from the group consisting of an organometallic compound (B-1), an organoaluminum oxy compound (B-2), and a compound (B-3) that reacts with the transition metal compound (A) to form an ion pair; A solid carrier (C) which is an inorganic compound; A method for producing an olefin polymerization catalyst, comprising: a step of contacting the transition metal complex (A) with the solid support (C) at a temperature below 20°C; 【Chemical 1】 (In the general formula [1], M′ is a transition metal atom of Group 4 of the periodic table, n' is an integer of 1 to 4 selected so that the transition metal compound (A) is electrically neutral; X' represents a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and 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, and when n is 2 or more, the multiple groups represented by X may be the same or different and may be bonded to each other to form a ring; Q' is an atom of Group 14 of the periodic table; R' 1 , R' 2 , R' 3 , R' 4 , R' 5 , R' 6 , R' 7 , R' 8 , R' 9 and R' 10 each independently represents 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' 1 ~R' 8 Adjacent substituents among these may be bonded to each other to form a ring which may have a substituent, R' 9 and R' 10 may be bonded to each other to form a ring containing Q′, and this ring may have a substituent.

2. 2. The method for producing an olefin polymerization catalyst according to claim 1, wherein the transition metal compound (A) is represented by the following general formula [2]: 【Chemistry 2】 (In the general formula [2], M is a transition metal atom of Group 4 of the periodic table, n is an integer of 1 to 4 selected so that the transition metal compound (A) is electrically neutral; X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and 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, and when n is 2 or more, the multiple groups represented by X may be the same or different and may be bonded to each other to form a ring; Q is an atom of Group 14 of the periodic table; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 each independently represents 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 1 ~R 6 Adjacent substituents among R may be bonded to each other to form a ring which may have a substituent, 7 ~R 12 Adjacent substituents among these may be bonded to each other to form a ring which may have a substituent, R 13 and R 14 may be bonded to each other to form a ring containing Q, and this ring may have a substituent.

3. In the general formula [2], M is a zirconium atom or a hafnium atom, X's each independently represent 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 6 and R 7 ~R 14 are each independently 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.

4. In the general formula [2], Q is a silicon atom; R 1 and R 6 is a hydrogen atom, R 2 ~R 5 and R 7 ~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, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms.

5. 2. The method for producing an olefin polymerization catalyst according to claim 1, wherein the solid support (C) is a porous oxide.

6. A method for producing an ethylene-based polymer, comprising polymerizing ethylene or polymerizing ethylene and an olefin having from 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst obtained by the method for producing an olefin polymerization catalyst according to any one of claims 1 to 5.

7. The method for producing an ethylene-based polymer according to claim 6, wherein the polymerization temperature is 0°C or higher.

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