Production method of preliminary polymerization catalyst used for olefin polymerization and production method of olefin polymer using the preliminary polymerization catalyst

Abstract

To provide a production method of a preliminary polymerization catalyst used for olefin polymerization which can prevent fouling in a reactor in production of the preliminary polymerization catalyst, and which can produce an olefin polymer showing stable and uniform physical properties and an olefin polymer with high molecular weight in production of the olefin polymer.SOLUTION: A production method of a preliminary polymerization catalyst (X) to be used for olefin polymerization comprises a step of supplying an olefin having 2 or more carbon atoms to a solid catalytic ingredient (Sa) including a transition metal complex (A) and a solid carrier (S) of 1 g at a speed of 1-10 L / hour in conditions of concentration of an organic aluminum compound except a solid content in a solvent of 0.1 mmol / L or more and 10 mmol / L or less and a preliminary polymerization temperature of 10-30°C for preliminary polymerization.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing a prepolymerization catalyst for olefin polymerization, which can prevent fouling in a reactor during the production of an olefin polymer, and can produce an olefin polymer that exhibits stable and uniform physical properties and an olefin polymer having a high molecular weight, and a method for producing an olefin polymer using the prepolymerization catalyst.

Background Art

[0002] Conventionally, as a catalyst for producing an olefin (co)polymer, an olefin polymerization catalyst composed of a transition metal complex such as zirconocene and a cocatalyst component such as an organoaluminum oxy compound (aluminoxane) is known. Among them, when slurry polymerization or gas-phase polymerization is carried out, generally, in order to improve the powder properties of the produced polymer, a solid catalyst in which a transition metal complex or an organoaluminum oxy compound is supported on a solid carrier such as silica gel is used (Non-Patent Document 1).

[0003] In addition, as a method for suppressing fouling in which a polymer adheres to the reactor wall surface and polymer lump formation in the reactor during the polymerization reaction, a method of prepolymerizing an olefin with a solid catalyst (Patent Document 1), a method of adding a specific compound to the reaction system (Patent Documents 2 and 3), etc. have been reported.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Non-Patent Documents

[0005]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, when an olefin is introduced in the presence of the above solid catalyst and a prepolymerization reaction is carried out, the solvent after the reaction may become turbid, and fouling in the reactor may be confirmed. Fouling reduces the heat removal efficiency from the reactor wall, making it difficult to control the reaction temperature and may lead to a decrease in productivity due to the cleaning of the reactor.

[0007] In addition, when producing an olefin polymer using a prepolymerization catalyst, if the hydrogen responsiveness of the prepolymerization catalyst is high, the physical properties of the olefin polymer may vary due to minute fluctuations in the hydrogen concentration, and it may not be possible to produce an olefin polymer that stably exhibits uniform physical properties. In particular, when polymerizing an olefin polymer, if the hydrogen concentration in the polymerization reactor is high, it may not be possible to produce an olefin polymer with a high molecular weight.

[0008] The present invention has been made to solve such problems. In the production of a prepolymerization catalyst, fouling in the reactor can be prevented, and in the production of an olefin polymer, it is an object of the present invention to provide a method for producing a prepolymerization catalyst for olefin polymerization that can produce an olefin polymer having stable and uniform physical properties and an olefin polymer having a high molecular weight.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved according to the following exemplary embodiments, and have completed the present invention. Exemplary embodiments of the present invention are shown below.

[0010] [1] A solid catalyst component (Sa) containing a transition metal complex (A) and a solid support (S) is A method for producing a prepolymerization catalyst (X) for olefin polymerization, comprising a step of prepolymerizing by supplying an olefin having 2 or more carbon atoms at a rate of 1 to 10 L / hr with respect to 1 g of the solid catalyst component (Sa) under the conditions that the concentration of the organoaluminum compound excluding the solid content in the solvent is 0.1 mmol / L or more and 10 mmol / L or less, and the prepolymerization temperature is 10 to 30 °C. [2] The method for producing a prepolymerization catalyst (X) according to item [1], wherein the prepolymerization amount of the olefin having 2 or more carbon atoms is 1 g or more and 50 g or less with respect to 1 g of the solid catalyst component (Sa). [3] The method for producing a prepolymerization catalyst (X) according to item [1] or [2], wherein the transition metal complex (A) contains a Group 4 transition metal atom of the periodic table, and the solid support (S) is a porous oxide. [4] The method for producing a prepolymerization catalyst (X) according to any one of items [1] to [3], wherein the prepolymerization catalyst (X) contains an organoaluminum oxy compound (B-2). [5] The method for producing a prepolymerization catalyst (X) according to any one of items [1] to [4], wherein the transition metal complex (A) is represented by the following general formula [1]. [Chemical formula] (In the general formula [1], M is a Group 4 transition metal atom of the periodic table, n is an integer of 1 to 4 selected so that the transition metal complex (A) is electrically neutral, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons. 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-based derivative group. When n is 2 or more, the groups represented by a plurality of Xs may be the same or different from each other, and may be bonded to each other to form a ring, Q is a Group 14 atom of the periodic table, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R7 , 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, R 1 ~R 6 Among adjacent substituents of these, they may be bonded to each other to form a ring which may have a substituent, R 7 ~R 12 Among adjacent substituents of these, they 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.) A method for producing an olefin polymer, characterized by polymerizing or copolymerizing an olefin in the presence of the prepolymerization catalyst (X) according to any one of items [1] to [5] of [6].

Effect of the Invention

[0011] According to the present invention, in the production of the prepolymerization catalyst, fouling in the reactor can be prevented, and in the production of the olefin polymer, a prepolymerization catalyst for olefin polymerization capable of producing an olefin polymer showing stable and uniform physical properties and an olefin polymer having a high molecular weight can be provided.

Mode for Carrying Out the Invention

[0012] Hereinafter, the method for producing a prepolymerization catalyst for olefin polymerization according to the present invention and the method for producing an olefin polymer using the catalyst will be specifically described. In the present invention, the term "polymerization" may be used in the sense of including not only the homopolymerization of olefins but also the copolymerization of two or more olefins, and the term "polymer" may be used in the sense of including not only homopolymers but also copolymers.

[0013] First, the components for forming the prepolymerization catalyst according to the present invention will be described below. In the method for producing a prepolymerization catalyst used in the olefin polymerization according to the present invention, the transition metal complex (A) and the solid carrier (S) constituting the solid catalyst component (Sa) are not particularly limited, but preferred examples are shown below.

[0014] <Transition metal complex (A)> The transition metal complex (A) used in the method for producing a prepolymerization catalyst according to the present invention is not particularly limited as long as it is a metallocene compound used as a catalyst for olefin polymerization, but preferably contains a Group 4 transition metal atom of the periodic table, and more preferably is represented by the following general formula [1].

[0015]

Chemical formula

[0016] 《M, n, X》 In general formula [1], M is a Group 4 transition metal atom of the periodic table, preferably a zirconium atom or a hafnium atom, and more preferably a zirconium atom.

[0017] n is an integer of 1 to 4 selected so that the transition metal complex (A) is electrically neutral, preferably 1 or 2, and more preferably 2. X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone pair of electrons, 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, and more preferably a halogen atom.

[0018] When n is 2 or more, a plurality of Xs may be the same as or different from each other, and may be bonded to each other to form a ring. When a plurality of the rings exist, the rings may be the same as or different from each other. Examples of the halogen atom include fluorine, chlorine, bromine, iodine, etc., preferably chlorine or bromine, and more preferably chlorine.

[0019] Examples of the hydrocarbon group include linear or branched alkyl groups such as methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group (butan-2-yl group), tert-butyl group (2-methylpropan-2-yl group), iso-butyl group (2-methylpropyl group), pentan-2-yl group, 2-methylbutyl group, iso-pentyl group (3-methylbutyl group), neopentyl group (2,2-dimethylpropyl group), siamyl group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group (2,3-dimethylbutan-2-yl group), 4,4-dimethylpentyl group, etc.; Vinyl group, allyl group, propenyl group (prop-1-en-1-yl group), iso-propenyl group (prop-1-en-2-yl group), arylenyl group (prop-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, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, iso-pentenyl group (3-methylbut-3-en-1-yl group), 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, prenyl group (3-methylbut-2-en-1-yl group), etc., linear or branched alkenyl groups or unsaturated double bond-containing groups; Ethynyl group, prop-2-yn-1-yl group, propargyl group (prop-1-yn-1-yl group), etc., linear or branched alkynyl groups or unsaturated triple bond-containing groups; Benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-iso-propylbenzyl group), 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group (diphenylmethyl group), etc., aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norbornenyl group, 1-adamantyl group, 2-adamantyl group, etc., cyclic saturated hydrocarbon groups; Aromatic substituents such as phenyl group, tolyl group (methylphenyl group), xylyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), duryl group (2,3,5,6-tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthylenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group, etc. are mentioned.

[0020] Among the hydrocarbon groups, methyl group, iso-butyl group, neopentyl group, silyl group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group are preferable.

[0021] Examples of the halogen-containing group include fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, hexachloroantimonate anion.

[0022] Among the halogen-containing groups, pentafluorophenyl group is preferable. Examples of the silicon-containing group include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, tris(trimethylsilyl)silyl group, trimethylsilylmethyl group, etc.

[0023] Among the silicon-containing groups, trimethylsilylmethyl group is preferable. Examples of the oxygen-containing group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, a benzyloxy group, a methoxymethoxy group, a phenoxy group, a 2,6-dimethylphenoxy group, a 2,6-di-iso-propylphenoxy group, a 2,6-di-tert-butylphenoxy group, a 2,4,6-trimethylphenoxy group, a 2,4,6-tri-iso-propylphenoxy group, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetoxy group, a perchlorate anion, and a periodate anion.

[0024] Among the oxygen-containing groups, a methoxy group, an ethoxy group, an iso-propoxy group, and a tert-butoxy group are preferable. Examples of the sulfur-containing group include a mesyl group (methanesulfonyl group), a phenylsulfonyl group, a tosyl group (p-toluenesulfonyl group), a triflyl group (trifluoromethanesulfonyl group), a nonaflyl group (nonafluorobutanesulfonyl group), a mesylate group (methanesulfonate group), a tosylate group (p-toluenesulfonate group), a triflate group (trifluoromethanesulfonate group), and a nonaflate group (nonafluorobutanesulfonate group).

[0025] Among the sulfur-containing groups, triflate (trifluoromethanesulfonate) is preferable. 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, and a bistriflylimide group.

[0026] Among the nitrogen-containing groups, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a pyrrolyl group, and a bistriflylimide group are preferable. Examples of the phosphorus-containing group include a hexafluorophosphate anion.

[0027] Examples of the boron-containing group include groups represented by tetrafluoroborate anion, tetrakis(pentafluorophenyl)borate anion, (methyl)(tris(pentafluorophenyl))borate anion, (benzyl)(tris(pentafluorophenyl))borate anion, tetrakis((3,5-bistrifluoromethyl)phenyl)borate anion, BR4 (where each R independently represents hydrogen, an alkyl group, an aryl group which may have a substituent, or a halogen atom, etc.). Examples of the aluminum-containing group include

[0028] [Chemical formula] (M represents M in the general formula (1).) Groups represented by AlR4 (where R represents hydrogen, an alkyl group, an aryl group which may have a substituent, or a halogen atom, etc.) that can form

[0029] Examples of the conjugated diene derivative group include 1,3-butadienyl group, isoprenyl group (2-methyl-1,3-butadienyl group), piperylenyl group (1,3-pentadienyl group), 2,4-hexadienyl group, 1,4-diphenyl-1,3-pentadienyl group, cyclopentadienyl group, etc., and metallocyclopentene group.

[0030] Examples of the neutral ligand capable of coordinating with an unshared electron pair include ethers such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, amines such as triethylamine, diethylamine, heterocyclic compounds such as pyridine, picoline, lutidine, oxazoline, oxazole, thiazole, imidazole, thiophene, and organic phosphorus compounds such as triphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine.

[0031] 《Q》 In the general formula [1], Q is an atom of Group 14 of the periodic table, for example, a carbon atom, a silicon atom, a germanium atom, or a tin atom, preferably a carbon atom or a silicon atom, and more preferably a silicon atom.

[0032] 《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.

[0033] R 1 ~R 14 Examples of the hydrocarbon group having 1 to 40 carbon atoms as R

[0034] include hydrocarbon groups having 1 to 20 carbon atoms. More specific examples include the specific examples of the hydrocarbon groups listed as examples of X above.

[0035] 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 substituents having an aromatic structure such as an arylalkyl group.

[0035] Examples of the hydrocarbon group having 1 to 40 carbon atoms include, for example, A linear or branched alkyl group having 1 to 40 carbon atoms such as methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, 1-nonyl group, 1-decanyl group, 1-undecanyl group, 1-dodecanyl group, 1-eicosanyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, pentan-2-yl group, 2-methylbutyl group, iso-pentyl group, neopentyl group, tert-pentyl group (1,1-dimethylpropyl group), siamyl group, pentan-3-yl group, 2-methylpentyl group, 3-methylpentyl group, iso-hexyl group, 1,1-dimethylbutyl group (2-methylpentan-2-yl group), 3-methylpentan-2-yl group, 4-methylpentan-2-yl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group, 3-methylpentan-3-yl group, 3,3-dimethylbutan-2-yl group, hexan-3-yl group, 2-methylpentan-3-yl group, heptan-4-yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,3,3-trimethylbutan-2-yl group, 2,4,4-trimethylpentan-2-yl group; A vinyl group, an allyl group, a propenyl group, an iso-propenyl group, an arylenyl group, a but-3-en-1-yl group, a crotyl group, a but-3-en-2-yl group, a methallyl group, a buta-1,3-dienyl group, a penta-4-en-1-yl group, a penta-3-en-1-yl group, a penta-2-en-1-yl group, an iso-pentenyl group, a 2-methylbut-3-en-1-yl group, a penta-4-en-2-yl group, a prenyl group, a 2-methyl-but-2-en-1-yl group, a penta-3-en-2-yl group, a 2-methyl-but-3-en-2-yl group, a penta-1-en-3-yl group, a penta-2,4-dien-1-yl group, a penta-1,3-dien-1-yl group, a penta-1,4-dien-3-yl group, an iso-prenyl group (2-methyl-but-1,3-dien-1-yl group), a penta-2,4-dien-2-yl group, a hexa-5-en-1-yl group, a hexa-4-en-1-yl group, a hexa-3-en-1-yl group, a hexa-2-en-1-yl group, a 4-methyl-penta-4-en-1-yl group, a 3-methyl-penta-4-en-1-yl group, a 2-methyl-penta-4-en-1-yl group, a hexa-5-en-2-yl group, a 4-methyl-penta-3-en-1-yl group, a 3-methyl-penta-3-en-1-yl group, a 2,3-dimethyl-but-2-en-1-yl group, a 2-methylpenta-4-en-2-yl group, a 3-ethylpenta-1-en-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-but-1,3-dien-1-yl group, a hexa-1,3,5-trien-1-yl group, a 2-(cyclopentadienyl)propan-2-yl group, a 2-(cyclopentadienyl)ethyl group, or other linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms; An ethynyl group, a prop-2-yn-1-yl group, a propargyl group, a but-1-yn-1-yl group, a but-2-yn-1-yl group, a but-3-yn-1-yl group, a pent-1-yn-1-yl group, a pent-2-yn-1-yl group, a pent-3-yn-1-yl group, a pent-4-yn-1-yl group, a 3-methyl-but-1-yn-1-yl group, a pent-3-yn-2-yl group, a 2-methyl-but-3-yn-1-yl group, 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, a hex-5-yn-1-yl group, or the like, a linear or branched alkynyl group or an unsaturated triple bond-containing group having 2 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, 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-iso-propylphenyl)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)diphenylmethyl group, 2-(tetrahydro-1-indacenyl)ethyl group, 2-(1-benzindenyl)propan-2-yl group, (1-benzindenyl)diphenylmethyl group, 2-(1-benzindenyl)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, 2-(1-azulenyl)ethyl group, etc., aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl 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, cyclooctatrienenyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, 7-methylbicyclo[2.2.1]heptan-7-yl group, bicyclo[2.2.2]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), 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, azulenyl group and other cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms; Aromatic substituents having 6 to 40 carbon atoms such as phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, duryl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, (buta-3-en-1-yl)phenyl group, (buta-2-en-1-yl)phenyl group, methallylphenyl group, prenylphenyl group, 4-adamantylphenyl group, 3,5-di-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthylenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group, etc. are exemplified.

[0036] Among the linear or branched alkyl groups having 1 to 40 carbon atoms, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, pentan-3-yl group, iso-hexyl group, 1,1-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group, 3-methylpentan-3-yl group, heptan-4-yl group, 2,4-dimethylpentan-2-yl group, 3-ethylpentan-3-yl group, 4,4-dimethylpentyl group, 4-methylheptan-4-yl group, 4-propylheptan-4-yl group, 2,4,4-trimethylpentan-2-yl group, etc. are preferable, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, iso-propyl group, tert-butyl group, neopentyl group, 2,4-dimethylpentan-2-yl group, 2,4,4-trimethylpentan-2-yl group are more preferable, and methyl group, ethyl group, iso-propyl group, tert-butyl group are even more preferable.

[0037] 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 hexa-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, etc. are preferable, and a vinyl group, an allyl group, a but-3-en-1-yl group, a pent-4-en-1-yl group, a prenyl group, a hexa-5-en-1-yl group are more preferable.

[0038] 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 pent-3-yn-1-yl group, a pent-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 hexa-4-yn-1-yl group, a hexa-5-yn-1-yl group, etc. are preferable, and a prop-2-yn-1-yl group, a propargyl group, a but-2-yn-1-yl group, a but-3-yn-1-yl group are more preferable.

[0039] 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-butylphenyl)ethyl group, 2-(3,5-di-tert-butylphenyl)ethyl group, styryl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group, neophyl group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, etc. are preferred, and benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 3-phenylpropyl group, cinnamyl group are more preferred.

[0040] Among the cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, pentalenyl group, indenyl group, fluorenyl group, etc. are preferable, and cyclopentyl group, cyclopentenyl group, 1-methylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-adamantyl group are more preferable.

[0041] Among the aromatic substituents having 6 to 40 carbon atoms, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, prenylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrocenyl group, etc. are preferable, and phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group are more preferable.

[0042] 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, 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, a trifluoromethylthio group, and the like.

[0043] 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 difluoromethylene dioxyphenyl group, a trifluoromethylthio group are preferable, and a trifluoromethyl group, a fluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a pentafluorobiphenyl group, a trifluoromethoxy group, a pentafluorophenoxy group are more preferable.

[0044] Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl 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 indenylmethylsilyl group, a di-n-butyl(indenyl)silyl group, an indenyl diphenylsilyl group, a fluorenyldimethylsilyl group, a di-n-butyl(fluorenyl)silyl group, a fluorenyldiphenylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-iso-propylsilylphenyl group, a 4-tert-butyldiphenylsilylphenyl group, a 4-triphenylsilylphenyl group, a 4-tris(trimethylsilyl)silylphenyl group, a 3,5-bis(trimethylsilyl)phenyl group, and the like.

[0045] Among these silicon-containing groups, trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, cyclopentadienyldimethylsilyl group, cyclopentadienyldiphenylsilyl group, indenylmethylsilyl group, indenylmethylsilyl group, fluorenyldimethylsilyl group, fluorenyldiphenylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 4-triphenylsilylphenyl group, 3,5-bis(trimethylsilyl)phenyl group and the like are preferable, and trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, 4-tri-iso-propylsilylphenyl group, 3,5-bis(trimethylsilyl)phenyl group are more preferable.

[0046] Examples of the oxygen-containing group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, a methallyloxy group, a prenyl-oxy group, a benzyloxy group, a methoxymethoxy group, a methoxyethoxy group, a phenoxy group, a naphthoxy group, a tolyloxy group, an iso-propylphenoxy group, an allylphenoxy group, a tert-butylphenoxy group, a methoxyphenoxy group, an iso-propoxyphenoxy 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 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, a dibenzofuryl group, etc.

[0047] Among these 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 prenyl oxy group, a benzyloxy group, a phenoxy group, a naphthoxy group, a toluoyloxy 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 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 tetrahydropyranyl group, a furofuryl group, a benzofuryl group, a dibenzofuryl group, etc. are preferable, and 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, a dibenzofuryl group are more preferable, and a methoxy group, a 3,5-di-tert-butyl-4-methoxyphenyl group are even more preferable.

[0048] Examples of the nitrogen-containing group include an amino group, dimethylamino group, diethylamino group, allylamino group, diallylamino group, didecylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, azepinyl group, dimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzylaminomethyl group, benzylaminoethyl group, pyrrolidinylethyl group, dimethylaminovinyl group, benzylaminovinyl group, pyrrolidinylvinyl group, dimethylaminopropyl group, benzylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, benzylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyldi julolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolyl group, phenylpyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group, and the like.

[0049] Among these nitrogen-containing groups, amino group, dimethylamino group, diethylamino group, allylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, dimethylaminomethyl group, benzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, pyrrolidinylethyl group, dimethylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyldujolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group, etc. are preferable, and amino group, dimethylamino group, diethylamino group, pyrrolidinyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyldujolidinyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group, imidazolyl group are more preferable.

[0050] 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 phenylthioallyl 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, a thiazolidinyl group, and the like.

[0051] 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 preferable.

[0052] R 1 ~R 6 Among the adjacent substituents of R 1 and R 2 R 2 and R 3 R 3 and R 4 R 4 and R 5 R 5 and R 6They may be bonded to each other to form a ring which may have a substituent. The ring formed in this case is preferably a 5- to 8-membered ring composed of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) or an unsaturated hydrocarbon which may have a substituent and is fused to the indenyl ring portion. When a plurality of rings exist, they may be the same as or different from each other. Although not particularly limited as long as the effects of the present invention are exhibited, the ring is more preferably a 5- or 6-membered ring. In this case, examples of the structure combining the ring and the indenyl ring portion of the parent nucleus include a substituted benzoindenyl ring, a substituted tetrahydroindacene ring, and a substituted cyclopentatetrahydronaphthalene. A substituted benzoindenyl ring and a substituted tetrahydroindacene ring are preferred.

[0053] R 7 ~R 12 Among the adjacent substituents of (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. The ring formed in this case is preferably a 5- to 8-membered ring composed of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) or an unsaturated hydrocarbon which may have a substituent and is fused to the indenyl ring portion. When a plurality of rings exist, they may be the same as or different from each other. Although not particularly limited as long as the effects of the present invention are exhibited, the ring is more preferably a 5- or 6-membered ring. In this case, examples of the structure combining the ring and the indenyl ring portion of the parent nucleus include a substituted benzoindenyl ring, a substituted tetrahydroindacene ring, a substituted cyclopentatetrahydronaphthalene, a substituted tetrahydrofluorene ring, and a substituted fluorene ring. A substituted benzoindenyl ring and a substituted tetrahydroindacene ring are preferred.

[0054] R 13 and R 14may 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 not particularly limited as long as the effects of the present invention are achieved, the ring is preferably a 4- to 6-membered ring. In this case, R 13 and R 14 As the structure of Q combined with, for example, a substituted cyclobutane ring, a substituted cyclopentane ring, a substituted fluorene ring, a substituted silacyclobutane (siletane) ring, a substituted silacyclopentane (silolane) ring, a substituted silacyclohexane (silinane), a substituted silafluorene ring can be mentioned, and a substituted cyclopentane ring, a substituted silacyclobutane ring, a substituted silacyclopentane ring are preferable.

[0055] 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.

[0056] R 2 ~ R 5 and R 7 ~ R 14 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. Note that, in at least one of R 7 R 9 and R 12 the oxygen-containing group, the nitrogen-containing group or the sulfur-containing group may be a heterocyclic aromatic group described later.

[0057] 《Preferred embodiments of the transition metal complex (A)》 As a preferred embodiment of the transition metal complex (A), In the general formula [1], M is a zirconium atom or a hafnium atom, X is, independently of one another, 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 8 ~R 14 are, independently of one another, 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, R 7 is a heterocyclic aromatic group which may have a substituent, having a 5-membered ring as a mother skeleton containing at least one atom selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or nitrogen, oxygen and sulfur, Transition metal complex (A-1) is exemplified, and as a more preferred embodiment, In the general formula [1], Q is a silicon atom, R 1 and R 6 are hydrogen atoms, R 2 ~R 5 and R 7 ~R 14 are, independently of one another, 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, Transition metal complex (A-2) is exemplified.

[0058] In the transition metal complex (A-1), examples of the heterocyclic aromatic group which may have a substituent, having a 5-membered ring (hereinafter also referred to as "hetero 5-membered ring") as a mother skeleton containing at least one atom selected from the group consisting of nitrogen, oxygen and sulfur, which is one of the options of R 7 , R 9 and R 12 include, for example, groups represented by the following general formulas [4a] to [4h].

[0059]

Chemical formula

[0060] In the general formulas [4a] to [4h], Ch is an oxygen atom or a sulfur atom, and R d is each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different from each other. In addition, the wavy lines in the general formulas [4a] to [4h] indicate the bonding sites with the indenyl ring.

[0061] Examples of the hydrocarbon group having 1 to 20 carbon atoms include the above-mentioned R 1 ~R 14Among the examples of the hydrocarbon group having 1 to 40 carbon atoms as described above, those having 1 to 20 carbon atoms are mentioned. Preferably, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, allyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctenyl group, norbornyl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 3-phenylpropyl group, cinnamyl group, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrocenyl group are mentioned. More preferably, methyl group, ethyl group, 1-propyl group, 1-butyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, allyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, biphenyl group, terphenyl group are mentioned.

[0062] R d are each independently an adjacent R dThey may be bonded to each other to form a saturated or unsaturated hydrocarbon group which, together with the atoms of the heterocyclic 5-membered ring moiety, may be fused to the heterocyclic 5-membered ring moiety to form a 5- to 8-membered ring, and which may have a substituent. 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, as a structure combining this ring and the heterocyclic 5-membered ring moiety of the parent nucleus, for example, a benzofuran ring, a benzothiophene ring, an indole ring, a carbazole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, a benzopyrazole ring, etc. can be mentioned.

[0063] Among the heterocyclic aromatic groups represented by the general formulas [4a] to [4h], the heterocyclic aromatic group represented by the general formula [4a] is preferred. Among the heterocyclic aromatic groups represented by the general formula [4a], a 2-furyl group, a 5-methyl-2-furyl group, a 2-thienyl group, and a 5-methyl-2-thienyl group are preferred.

[0064] 《Examples of the transition metal complex (A)》 Specific examples of the transition metal complex (A) are shown below, but the scope of the present invention is not particularly limited thereby.

[0065] For convenience, the ligand structure excluding the portion represented by MXn (metal portion) of the transition metal complex (A) is divided into seven structures of the 2-indenyl ring portion, the 1-indenyl ring portion, the indenyl ring portion R 1 , R 6 and R 8 substituents, the indenyl ring portion R 2 , R 5 , R 9 , and R 12 substituents, the indenyl ring portion R 3 , R 4 , R 10 , and R 11 substituents, the 1-indenyl ring portion R 7 substituents, and the structure of the bridging portion. The abbreviation of the 2-indenyl ring portion is α, the abbreviation of the 1-indenyl ring portion is β, and the indenyl ring portion R 1 , R 6 and R 8The abbreviation of the substituent is γ, and the indenyl ring moiety R 2 、R 5 、R 9 、and R 12 The abbreviation of the substituent is δ, and the indenyl ring moiety R 3 、R 4 、R 10 、and R 11 The abbreviation of the substituent is ε, and the 1-indenyl ring moiety R 7 The abbreviation of the substituent is ζ, the abbreviation of the structure of the crosslinking moiety is η, and the abbreviations of each substituent are shown in [Table 1] to [Table 7].

[0066]

Table 1

[0067]

Table 2

[0068]

Table 3

[0069]

Table 4

[0070]

Table 5

[0071] [Table 6]

[0072] [Table 7]

[0073] 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-Si(Me)3)2, Ti(ОMe)2, Ti(ОiPr)2, Ti(NMe2)2, Ti(ОMs)2, Ti(ОTs)2, Ti(ОTf)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(ОMe)2, Zr(ОiPr)2, Zr(NMe2)2, Zr(ОMs)2, Zr(ОTs)2, Zr(ОTf)2, HfF2, HfCl2, HfBr2, HfI2, Hf(Me)2, Hf(Bn)2, Hf(Allyl)2, Hf(CH2-tBu)2, Hf(1,3-butadienyl), Hf(1,3-pentadienyl), Hf(2,4-hexadienyl), Hf(1,4-diphenyl-1,3-pentadienyl), Hf(CH2-Si(Me)3)2, Hf(ОMe)2, Hf(ОiPr)2, Hf(NMe2)2, Hf(ОMs)2, Hf(ОTs)2, Hf(ОTf)2, etc. Me is a methyl group, Bn is a benzyl group, tBu is a tert-butyl group, Si(Me)3 is a trimethylsilyl group, ОMe is a methoxy group, ОiPr is an iso-propoxy group, NMe2 is a dimethylamino group, ОMs is a methanesulfonate group, ОTs is a p-toluenesulfonate group, and ОTf is a trifluoromethanesulfonate group.

[0074] According to the above notations, the 2-indenyl ring moiety is α-1 in [Table 1], the 1-indenyl ring moiety is β-5 in [Table 2], and the indenyl ring moieties R 1 , R 6 and R 8 substituents are all γ-1 in [Table 3], and the 2-indenyl ring moieties R 2 and R 5All substituents are the δ-1, 2-indenyl ring moiety R in [Table 4] 3 and R 4 All substituents are the ε-1, 1-indenyl ring moiety R in [Table 5] 7 The substituents are the ζ-30, 1-indenyl ring moiety R in [Table 6] 9 The substituents are the δ-38, 1-indenyl ring moiety R in [Table 4] 12 When the combination is such that the substituents are those in δ-3 in [Table 4] and the bridging moiety is η-20 in [Table 7], and MXn of the metal moiety is ZrCl2, the compound represented by the following formula [5] is exemplified.

[0075]

Chemical formula

[0076] Also, when the 2-indenyl ring moiety is α-1 in [Table 1], the 1-indenyl ring moiety is β-2 in [Table 2], the indenyl ring moieties R 1 , R 6 and R 8 All substituents are the γ-1, 2-indenyl ring moiety R in [Table 3] 2 and R 5 All substituents are the δ-2, 2-indenyl ring moiety R in [Table 4] 3 and R 4 All substituents are the ε-1, 1-indenyl ring moiety R in [Table 5] 7 When the combination is such that the substituents are those in ζ-1 in [Table 6] and the bridging moiety is η-4 in [Table 7], and MXn of the metal moiety is Zr(NMe2)2, the compound represented by the following formula [6] is exemplified.

[0077]

Chemical formula

[0078] Also, when the 2-indenyl ring moiety is α-3 in [Table 1], the 1-indenyl ring moiety is β-1, the 2-indenyl ring moieties R 1 and R 6 All substituents are the γ-2, indenyl ring moiety R in [Table 3] 2 , R5 and R 12 wherein all of the substituents are the δ-1, 1-indenyl ring moiety R in [Table 4] 7 wherein the substituent is the ζ-12, 1-indenyl ring moiety R in [Table 6] 8 wherein the substituent is the γ-1, 1-indenyl ring moiety R in [Table 3] 9 wherein the substituent is the δ-42, 1-indenyl ring moiety R in [Table 4] 10 wherein the substituent is the ε-3, 1-indenyl ring moiety R in [Table 5] 11 wherein the substituent is the ε-12 in [Table 5], the bridging moiety is the η-31 in [Table 7], and when MXn of the metal moiety is HfMe2, the compound represented by the following formula [7] is exemplified.

[0079] [Chemical formula]

[0080] Also, the 2-indenyl ring moiety is α-1 in [Table 1], the 1-indenyl ring moiety is β-1 in [Table 2], the 2-indenyl ring moiety R 1 and R 6 wherein all of the substituents are the γ-1, 2-indenyl ring moiety R in [Table 3] 2 wherein the substituent is the δ-7, 2-indenyl ring moiety R in [Table 4] 3 , R 4 , R 10 and R 11 wherein all of the substituents are the ε-1, 2-indenyl ring moiety R in [Table 5] 5 wherein the substituent is the δ-2, 1-indenyl ring moiety R in [Table 4] 7 wherein the substituent is the ζ-1, 1-indenyl ring moiety R in [Table 6] 8 wherein the substituent is the γ-9, 1-indenyl ring moiety R in [Table 3] 9 and R 12 wherein all of the substituents are the δ-1 in [Table 4], the bridging moiety is the η-29 in [Table 7], and when MXn of the metal moiety is Ti(1,3-pentadienyl), the compound represented by the following formula [8] is exemplified.

[0081] [Chemical formula]

[0082] Further, in the transition metal complex (A), there are two directions of the plane of the indenyl ring portion that binds to the central metal with the bridging portion interposed therebetween (front surface and back surface). Therefore, when there is no plane of symmetry in the 2-indenyl ring portion, there are, for example, two types of structural isomers represented by the following general formula [9a] or [9b].

[0083]

Chemical formula

[0084]

Chemical formula

[0085] Purification, separation, or selective production of these structural isomer mixtures is possible by known methods, and the production method is not particularly limited. Known production methods include, in addition to those mentioned as the production method of the transition metal complex (A), the production methods disclosed in JP-A-10-109996, "Organometallics 1999, 18, 5347.", "Organometallics 2012, 31, 4340.", JP-T-2011-502192, etc.

[0086] In addition, within the range of the transition metal complex (A), the transition metal complex may be used alone, two or more thereof may be used in combination, a mixture of structural isomers may be used, a structural isomer may be used alone, or a mixture of two or more structural isomers may be used. As described above, according to the present invention, an ethylene-based polymer having a large number of long-chain branches introduced can be produced with high catalytic activity using only the transition metal complex (A) as the transition metal complex used in the method for producing a prepolymerization catalyst. However, within a range where this effect is not impaired, one or more transition metal complexes different from the transition metal complex (A) may be used in combination as the transition metal complex. At this time, the transition metal complex (A) may be in any of the above-described embodiments.

[0087] 《Method for Producing Transition Metal Complex (A)》 The transition metal complex (A) can be produced using a conventionally known method. Examples of typical synthetic routes are shown below, but the production method is not particularly limited. In the following [Formula 1] to [Formula 5], R 1 ~R 14 , Q, M, X, and n have the same meanings as those described in the above general formula [1].

[0088] The substituted indene compound as the starting material can be produced by a known method, and the production method is not particularly limited. Examples of known production methods include those disclosed in “Organometallics 1994, 13, 954.”, “Organometallics 2006, 25, 1217.”, JP-T-2006-509059, “Bioorg. Med. Chem. 2008, 16, 7399.”, WO2009 / 080216, “Organometallics 2011, 30, 5744.”, JP-T-2011-500800, “Organometallics 2012, 31, 4962.”, “Chem. Eur. J. 2012, 18, 4174.”, JP-A-2012-012307, JP-A-2012-121882, JP-A-2014-196319, JP-T-2014-513735, JP-A-2015-063495, JP-A-2016-501952, etc.

[0089] Among the above-mentioned substituted indene compounds, those unsubstituted at the 2-position can be brominated at the 2-position by the following known methods, and the production method is not particularly limited.

[0090]

Chemical formula

[0091] In the above [Formula 1], NBS represents N-bromosuccinimide, and PTSA represents p-toluenesulfonic acid or its monohydrate. There are 5-membered ring partial double bond position isomers in the indene compound, and a mixture of these isomers may also be used. As known production methods, for example, in addition to the JP-A-2012-121882 and JP-A-2015-063495 disclosed above, the production methods disclosed in JP-A-2014-111568 and the like can be mentioned.

[0092] The above-mentioned 2-brominated substituted indene compound and 4-brominated substituted indene compound can produce the corresponding coupling product by a known method such as the Suzuki-Miyaura coupling reaction using the following palladium catalyst, and the production method is not particularly limited.

[0093]

Chemical formula

[0094] Similarly, there are 5-membered ring partial double bond position isomers in the indene compound, and a mixture of these isomers may also be used. In addition, various boronic acid esters, boroxines and other boron compounds may be used instead of the boronic acid, and the reaction mixture of the halogen compound and the metal reagent and then the boron compound may be used without isolation and purification. A nickel catalyst or an iron catalyst may be used instead of the palladium catalyst. As known production methods, for example, in addition to those shown above, JP-A-2014-196274 and the like can be mentioned.

[0095] In addition, for the production of the coupling product, instead of the Suzuki-Miyaura coupling with a boron compound, a Negishi coupling with an organozinc reagent, a Mizoroki-Heck reaction with an alkene compound, a Hiyama coupling with an organosilicon compound, a Sonogashira-Hagiwara coupling with a terminal alkyne compound, a Migita-Kosugi-Stille coupling with an organotin compound, a Kumada-Tamao-Corriu coupling with an organomagnesium compound, a Buchwald-Hartwig coupling, a Goldberg amination reaction, or a Ullmann ether synthesis reaction may be used. As known production methods, for example, in addition to those shown above, JP-A-8-183814, JP-T-2005-529865, JP-T-2006-509046, etc. can be mentioned.

[0096] For the production of the coupling product, the unsubstituted indene compound at the 2-position and an aromatic halide may be used, and a known method such as a direct coupling reaction using a palladium catalyst may be employed.

[0097]

Chemical formula

[0098] In the above [Formula 3], Ar represents an aromatic substituent, and a mixture of indene compound 5-membered ring partial double bond position isomers may be used. As known production methods, for example, JP-T-2000-512661, JP-A-2014-201519, etc. can be mentioned. The transition metal complex (A) and the precursor compound (ligand) can be produced by known methods using various substituted indene compounds produced by the above methods and the like. When Q is a silicon atom, a germanium atom, or a tin atom, it can be produced by the following methods, and the production method is not particularly limited.

[0099]

Chemical formula

[0100] In the above [Formula 4], in the synthesis of the precursor compound (ligand), the organomagnesium reagent prepared from the 2-brominated substituted indene compound and the organolithium reagent prepared from the substituted 1-indene compound preferably react stepwise with the chloride containing Q, and the order may be either. After the reaction with the organometallic reagent in the first step, the by-produced inorganic compound may be removed under an inert atmosphere, or the reaction product may be isolated by operations such as distillation, crystallization or washing and then used. In the reaction with the organometallic reagent in the second step, it is preferable to add 0.1 to 5.0 equivalents of DMI (1,3-dimethyl-2-imidazolidinone), DMPU (N,N'-dimethylpropyleneurea) or HMPA (hexamethylphosphoric triamide) etc. to the organometallic reagent, more preferably DMI and it is 1.0 equivalent. In addition, although there are indene compound 5-membered ring partial double bond position isomers in the substituted indene compound and the precursor compound (ligand), a mixture of these isomers may also be used.

[0101] As known production methods of the transition metal complex (A) and the precursor compound (ligand), for example, in addition to those shown above, JP-A-11-315089, JP-A-2001-302687, JP-A-2001-220404, "Polymer Journal 2002, 59, 243.", JP-T-2003-522194, "Macromolecules 2004, 37, 2342.", JP-A-2007-320935, JP-A-2011-126813 etc. can be mentioned.

[0102] When Q is a carbon atom, it can be produced by the following methods, and the production method is not particularly limited.

[0103]

Chemical formula

[0104] In the above [Formula 5], base is a basic substance capable of generating indenyl anion, such as sodium hydride, n-butyllithium, an organometallic compound such as Grignard reagent, an inorganic base such as sodium hydroxide or potassium hydroxide, and an organic base such as diethylamine or pyrrolidine, but is not particularly limited. In the presence of a basic substance, a fulvene compound can be synthesized from a substituted 1-indenecarbonyl compound and a carbonyl compound by a known method, and a precursor compound (ligand) can be produced by reacting an organomagnesium reagent prepared from a 2-brominated substituted indenecarbonyl compound. It should be noted that the substituted indenecarbonyl compound and the precursor compound (ligand) have indenecarbonyl compound 5-membered ring partial double bond position isomers, and a mixture of these isomers may also be used.

[0105] As known production methods of the transition metal complex (A) and the precursor compound (ligand), for example, in addition to those shown above, there are "Macromolecules 2003, 36, 9325.", "Organometallics 2004, 23, 5332.", "Eur. J. Inorg. Chem. 2005, 1003.", "Eur. J. Inorg. Chem. 2009, 1759.", etc.

[0106] <Solid support (S)> The solid support (S) according to the present invention is an inorganic or organic compound and is a granular or particulate solid. Among these, examples of the inorganic compound include a porous oxide, an inorganic halide, clay, a clay mineral or an ion-exchangeable layered compound, and examples of the inorganic halide include a porous oxide and an inorganic chloride as described below. When the transition metal complex (A) contains a Group 4 transition metal atom of the periodic table, it is preferable that the solid support (S) is a porous oxide from the viewpoint that the morphology of the olefin polymer can be improved and the olefin polymer can be produced with high productivity.

[0107] As the porous oxide, specifically, SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc., or a composite or mixture containing these can be used. For example, natural or synthetic zeolite, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc. can be used. Among these, those with SiO2 as the main component are preferred.

[0108] In addition, the above inorganic oxides may contain a small amount of carbonates, sulfates, nitrates, and oxide components such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, Li2O, etc.

[0109] Although the properties of such porous oxides vary depending on the type and manufacturing method, as the solid carrier used in the present invention, the particle size is usually 0.2 to 300 μm, preferably 1 to 200 μm, more preferably 20 to 100 μm, and even more preferably 40 to 80 μm, and the specific surface area is usually 50 to 1200 m 2 / g, preferably 100 to 1000 m 2 / g, more preferably 200 to 600 m 2 / g, and even more preferably 300 to 400 m 2 / g, and the pore volume is usually 0.3 to 30 cm 3 / g, preferably 0.5 to 10 cm 3 / g, more preferably 0.8 to 5 cm 3 / g, and even more preferably 1.0 to 2.0 cm 3 / g. Such a carrier is preferably used after being calcined at, for example, 100 to 1000 °C, preferably 150 to 700 °C, more preferably 175 to 500 °C, and even more preferably 200 to 300 °C, as needed.

[0110] As the inorganic halide, MgCl2, MgBr2, MnCl2, MnBr2, etc. are used. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Also, after dissolving the inorganic halide in a solvent such as alcohol, a precipitate obtained by precipitation into fine particles with a precipitant can be used.

[0111] Clay is usually composed mainly of clay minerals. Also, an ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds or the like are stacked parallel to each other with a weak binding force, and the contained ions are exchangeable. Most clay minerals are ion-exchangeable layered compounds. Also, as these clays, clay minerals, and ion-exchangeable layered compounds, not limited to naturally occurring ones, synthetic products can also be used.

[0112] Also, examples of the clay, clay mineral, or ion-exchangeable layered compound include clay, clay mineral, and ion-crystalline compounds having a layered crystal structure such as hexagonal close packing type, antimony type, CdCl2 type, CdI2 type, etc.

[0113] Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrolite clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudite group, palygorskite, kaolinite, nacrite, dickite, halloysite, etc. Examples of the ion-exchangeable layered compound include crystalline acidic salts of polyvalent metals such as α-Zr(HAsO4)2·H2O, α-Zr(HPO4)2, α-Zr(KPO4)2·3H2O, α-Ti(HPO4)2, α-Ti(HAsO4)2·H2O, α-Sn(HPO4)2·H2O, γ-Zr(HPO4)2, γ-Ti(HPO4)2, γ-Ti(NH4PO4)2·H2O, etc.

[0114] Such a clay, clay mineral, or ion-exchangeable layered compound preferably has a pore volume of 0.1 cm 3 / g or more with a pore radius of 20 Å or more measured by the mercury intrusion method, and 0.3 to 5 cm3 Those with a pore volume of / g are particularly preferred. Here, the pore volume is measured by mercury intrusion method using a mercury porosimeter in the range of pore radius from 20 Å to 3×10 4 Å.

[0115] When the pore volume with a pore radius of 20 Å or more is less than 0.1 cm 3 / g is used as the carrier, it tends to be difficult to obtain high polymerization activity. It is also preferable to subject clay and clay minerals to chemical treatment. As the chemical treatment, any of surface treatment for removing impurities adhering to the surface, treatment affecting the crystal structure of clay, etc. can be used. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment, etc. can be mentioned. Acid treatment not only removes surface impurities but also increases the surface area by eluting cations such as Al, Fe, Mg, etc. in the crystal structure. In alkali treatment, the crystal structure of clay is destroyed, resulting in a change in the structure of clay. Also, in salt treatment and organic matter treatment, ion complexes, molecular complexes, organic derivatives, etc. can be formed to change the surface area and interlayer distance.

[0116] The ion-exchangeable layered compound may be a layered compound in a state where the interlayer is expanded by utilizing the ion-exchangeability and exchanging the exchangeable ions in the interlayer with another large and bulky ion. Such a bulky ion plays a pillar-like role in supporting the layered structure and is usually called a pillar. Also, introducing another substance into the interlayer of the layered compound in this way is called intercalation. As the guest compound for intercalation, cationic inorganic compounds such as TiCl4, ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, B(OR)3 (R is a hydrocarbon group, etc.), [Al 13 O4(OH) 24 7+ 、[Zr4(OH) 14 2+ 、[Fe3O(OCOCH3)6] + ​​Examples include metal hydroxide ions and the like. These compounds can be used alone or in combination of two or more. When intercalating these compounds, polymers obtained by hydrolyzing metal alkoxides such as Si(OR)4, Al(OR)3, Ge(OR)4 (where R is a hydrocarbon group or the like), colloidal inorganic compounds such as SiO2, etc. can also coexist. Also, examples of the pillar include oxides formed by heating and dehydrating after intercalating the above metal hydroxide ions between layers.

[0117] Clay, clay minerals, and ion-exchange layered compounds may be used as they are, or may be used after treatments such as ball milling and sieving. Also, they may be used after newly adsorbing water or after heat dehydration treatment. Further, they may be used alone or in combination of two or more.

[0118] Examples of the organic compound include granular or particulate solids having a particle size in the range of 1 to 300 μm. Specifically, (co)polymers mainly composed of olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, (co)polymers mainly composed of vinylcyclohexane, styrene, divinylbenzene, and modified products thereof can be exemplified.

[0119] Also, those obtained by contacting the above inorganic or organic compound with component (B) described later, and solid components obtained by insolubilizing component (B) described later by the methods described in JP-A-11-140113, JP-A-2000-38410, JP-A-2000-95810, International Publication WO2010 / 55652 pamphlet, etc. can also be used as the solid support (S).

[0120] <Component (B)> The solid catalyst component (Sa) according to the present invention can further use component (B) described below, if necessary, in addition to the above transition metal complex (A) and the above solid support (S).

[0121] Component (B) that can be used in the present invention is at least one compound selected from the group consisting of the following (B-1) to (B-3). (B-1) An organometallic compound represented by the following general formula (II), (III) or (IV), R d m Al(OR e ) n H p X q ···(II) 〔In general formula (II), R d and R e represent hydrocarbon groups having 1 to 15 carbon atoms, and may be the same or different from each other. X represents a halogen atom, m is 0 < m ≦ 3, n is 0 ≦ n < 3, p is 0 ≦ p < 3, q is 0 ≦ q < 3, and m + n + p + q = 3.〕 M a AlR f 4···(III) 〔In general formula (III), M a represents Li, Na or K, and R f represents a hydrocarbon group having 1 to 15 carbon atoms.〕 R g r M b R h s X t ···(IV) 〔In general formula (IV), R g and R h represent hydrocarbon groups having 1 to 15 carbon atoms, and may be the same or different from each other. M b represents Mg, Zn or Cd, X represents a halogen atom, r is 0 < r ≦ 2, s is 0 ≦ s ≦ 1, t is 0 ≦ t ≦ 1, and r + s + t = 2.〕

[0122] (B-2) An organoaluminum oxy compound, and (B-3) A compound that reacts with the transition metal complex (A) to form an ion pair, is at least one compound selected from

[0123] In the above general formula (II), R d and Re may be the same as or different from each other. Examples of the hydrocarbon group include, for example, an alkyl group, a cycloalkyl group, and an aryl group. Specifically, they are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a tolyl group, etc. Preferably, they are an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.

[0124] Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. In the above general formula (III), R f Examples of the hydrocarbon group of are the same hydrocarbon groups as those of the above R d and R e are exemplified.

[0125] In the above general formula (IV), R g and R h may be the same as or different from each other. Examples of the hydrocarbon group include the same hydrocarbon groups as those of the above R d and R e are exemplified. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

[0126] Among the organometallic compounds (B-1) represented by the general formula (II), (III) or (IV), those represented by the general formula (II) are preferred. Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum ; and alkylaluminum hydrides such as dimethylaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, and diisohexylaluminum hydride, etc. These are used alone or in combination of two or more.

[0127] As the organoaluminum oxy compound (B-2), an organoaluminum oxy compound prepared from trialkylaluminum or tricycloalkylaluminum is preferable, an aluminoxane prepared from trimethylaluminum or triisobutylaluminum is more preferable, and an aluminoxane prepared from trimethylaluminum is even more preferable. Incidentally, the aluminoxane prepared from trimethylaluminum is also called methylaluminoxane or MAO. Such an organoaluminum oxy compound is used alone or in combination of two or more.

[0128] As the compound (B-3) that reacts with the transition metal complex (A) to form an ion pair, Lewis acids, ionic compounds, borane compounds, and carborane compounds described in 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 US5321106, etc., and furthermore, heteropoly compounds and isopoly compounds can be used without limitation.

[0129] In the present invention, when an organoaluminum oxy compound (B-2) such as aluminoxane is used as a cocatalyst component in addition to the transition metal complex (A), very high polymerization activity is exhibited. Therefore, it is preferable to use the organoaluminum oxy compound (B-2) as the component (B).

[0130] <Method for producing prepolymerization catalyst (X)> The method for producing the prepolymerization catalyst (X) used in the olefin polymerization according to the present invention comprises a step of prepolymerizing the solid catalyst component (Sa) containing the transition metal complex (A) and the solid carrier (S) under the conditions that the concentration of the organoaluminum compound excluding the solid content in the solvent is 0.1 mmol / L or more and 10 mmol / L or less, and the prepolymerization temperature is 10 to 30°C, and an olefin having 2 or more carbon atoms is supplied at a rate of 1 to 10 L / hr per 1 g of the solid catalyst component (Sa). By adopting the method for producing the prepolymerization catalyst (X) of the present invention, fouling in the prepolymerization reactor can be suppressed, an olefin polymer with stable and uniform physical properties can be produced, and an olefin polymer with a high molecular weight can be produced.

[0131] <Solid catalyst component (Sa)> The solid catalyst component (Sa) used in the method for producing the prepolymerization catalyst (X) of the present invention is obtained by contacting the solid carrier (S) and the transition metal complex (A) in an inert hydrocarbon at a temperature of -50°C or higher and 200°C or lower, preferably -20°C or higher and 150°C or lower, more preferably 0°C or higher and 100°C or lower, and even more preferably 15°C or higher and 30°C or lower. The contact time is 0.01 to 48 hours, preferably 0.1 to 24 hours, more preferably 0.3 to 6 hours, and even more preferably 0.5 to 2 hours.

[0132] Specific examples of the inert hydrocarbon used in the preparation of the solid catalyst component (Sa) 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; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof.

[0133] When two or more transition metal complexes (A) are used, the order of contact with the solid carrier (S) is arbitrary, and the two or more transition metal complexes (A) may be contacted in any order or simultaneously.

[0134] When preparing the solid catalyst component (Sa), the transition metal complex (A) is usually used in an amount of 1 μmol to 1.0 mmol, preferably 3 μmol to 0.5 mmol, more preferably 5 μmol to 0.3 mmol, and even more preferably 10 μmol to 0.1 mmol per 1 g of the solid carrier (S).

[0135] Here, in the preparation of the solid catalyst component (Sa) according to the present invention, the above component (B) can be preferably used in combination. The mode is not limited in any way, but examples of preferred modes are shown below.

[0136] (i) A method of preparing the solid catalyst component (Sa) by mixing and contacting a solid carrier (S) and component (B), and then contacting the transition metal complex (A). (ii) A method of preparing the solid catalyst component (Sa) by mixing and contacting the transition metal complex (A) and component (B), and then contacting the solid carrier (S).

[0137] The contact between component (B) and the solid carrier (S) is preferably carried out in an inert hydrocarbon solvent. Examples of the inert hydrocarbon solvent include the same ones as those used in the preparation of the solid catalyst component (Sa). The contact time between component (B) and the solid carrier (S) is usually 0.1 to 48 hours, preferably 0.5 to 20 hours, more preferably 1 to 12 hours, and still more preferably 3 to 6 hours. The contact temperature is usually -50 to 200°C, preferably -20 to 120°C, more preferably -10 to 110°C, and still more preferably -5 to 100°C. The contact molar ratio of component (B) to the solid carrier (S) (component (B) / solid carrier (S)) is usually 0.1 to 1000, preferably 0.1 to 100.

[0138] <Prepolymerization catalyst (X)> The prepolymerization catalyst (X) according to the present invention can be obtained by prepolymerizing the prepolymerization catalyst (Sa) under the above conditions.

[0139] The solvent used in the preparation of the prepolymerization catalyst (X) is preferably an inert hydrocarbon solvent. Examples of the inert hydrocarbon solvent include the same ones as those used when preparing the solid catalyst component (Sa).

[0140] The prepolymerization can be carried out by any of the batch, semi - continuous, and continuous methods, and can also be carried out under reduced pressure, normal pressure, or increased pressure. The concentration of the solid catalyst component (Sa) in the prepolymerization system is usually 1 - 1000 g / L, preferably 5 - 500 g / L, more preferably 10 - 200 g / L, and still more preferably 20 - 100 g / L in terms of the ratio of the solid catalyst component (Sa) to 1 liter of the polymerization volume.

[0141] The organoaluminum compound used in the present invention is not limited in any way, but preferably includes the general formulas (II) and (III) of component (B - 1) or component (B - 2). The concentration of the organoaluminum compound is in the range of 0.1 mmol / L or more and 10 mmol / L or less, preferably 0.3 mmol / L or more and 5.0 mmol / L or less, more preferably 0.5 mmol / L or more and 2.0 mmol / L or less, and still more preferably 1.0 mmol / L or more and 1.5 mmol / L or less, excluding the solid content derived from the solid catalyst component (Sa). When the concentration of the organoaluminum compound is within the above - mentioned range, it is preferable in that an olefin polymer with a high molecular weight can be produced.

[0142] The prepolymerization temperature is usually 10 - 30°C, preferably 15 - 30°C, and the prepolymerization time is usually 0.5 - 100 hours, preferably about 1 - 50 hours. When the prepolymerization temperature is within the above - mentioned range, it is preferable in that fouling in the reactor can be suppressed in the production of the prepolymerization catalyst.

[0143] The supply rate of the olefin having 2 or more carbon atoms for prepolymerization is usually 1 - 10 L / hr, preferably 1 - 7 L / hr, more preferably 1 - 4 L / hr per 1 g of the solid catalyst component (Sa).

[0144] The amount of the olefin having 2 or more carbon atoms for prepolymerization is preferably 1 g or more and 50 g or less, more preferably 1.5 g or more and 30 g or less, and still more preferably 2 g or more and 20 g or less per 1 g of the solid catalyst component (Sa). If the prepolymerization amount of an olefin having 2 or more carbon atoms is small, the release of the transition metal component from the solid catalyst component (Sa) is promoted in the subsequent polymerization reaction. If the prepolymerization amount is large, electrostatic adhesion is likely to occur during prepolymerization due to the charging of the prepolymerization component.

[0145] Examples of the olefin having 2 or more carbon atoms used during prepolymerization include α-olefins having 2 to 20 carbon atoms. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. are exemplified. Among these, ethylene and propylene are preferred, and ethylene is more preferred.

[0146] In addition, polymerization can also proceed by coexisting at least one selected from cyclic olefins and aromatic vinyl compounds in the reaction system. It is also possible to use a diene in combination. Also, other components such as vinylcyclohexane may be copolymerized without departing from the spirit of the present invention. With respect to 100 parts by mass of the α-olefin having 2 to 20 carbon atoms, other monomers can be used in an amount of, for example, 20 parts by mass or less, preferably 10 parts by mass or less.

[0147] Examples of the cyclic olefin include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

[0148] Examples of the aromatic vinyl compound include styrene; mono- or polyalkylstyrenes such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene.

[0149] Examples of the diene include α,ω-non-conjugated dienes such as 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene; non-conjugated dienes such as ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene; and conjugated dienes such as butadiene and isoprene.

[0150] The prepolymerization catalyst (X) obtained by the above production method may be used for olefin polymerization as a suspension, or after separation from the suspension, it may be suspended again in an inert hydrocarbon and used for olefin polymerization, or after drying, it may be used for olefin polymerization.

[0151] In the production of the prepolymerization catalyst (X) according to the present invention, the following component (G) may be added (and contacted) before, during, or after the step of producing the prepolymerization catalyst (X) according to the present invention.

[0152] <Component (G)> The component (G) that can be used as required in the present invention is usually a compound called a surfactant, and specifically, at least one compound selected from the group consisting of the following (g-1) to (g-6) is included. (g-1) Polyalkylene oxide block, (g-2) Higher aliphatic amide, (g-3) Polyalkylene oxide, (g-4) Polyalkylene oxide alkyl ether, (g-5) Alkyldiethanolamine, and (g-6) Polyoxyalkylene alkylamine.

[0153] Component (G) can be coexisted in the olefin polymerization catalyst for the purpose of suppressing fouling in the polymerization reactor by electrostatic adhesion of the catalyst or polymer, or improving the particle properties of the produced polymer. Among components (G), (g-1), (g-2), (g-3) and (g-4) are preferred, and (g-1) and (g-2) are particularly preferred. Specific examples of (g-2) include higher fatty acid diethanolamide and the like.

[0154] <Process for producing olefin polymer> The prepolymerization catalyst (X) according to the present invention can be used for the production of olefin homopolymers or olefin copolymers having 2 or more carbon atoms, such as ethylene, propylene, 1-butene, 1-octene, 4-methyl-1-pentene and the like.

[0155] Hereinafter, the process for producing an olefin polymer according to the present invention will be described with respect to the process for producing an ethylene-based polymer, which is a representative example of the olefin polymer. A preferred ethylene-based polymer obtained by the process for producing an olefin polymer according to the present invention is a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms. Examples of the α-olefin having 3 to 10 carbon atoms used for copolymerization with ethylene include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and the like.

[0156] In the method for producing an olefin polymer of the present invention, the polymerization of olefins can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization or gas phase polymerization methods. Examples of the inert hydrocarbon medium 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; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. The inert hydrocarbon medium may be used alone or in combination of two or more. Also, a so-called bulk polymerization method can be used in which the liquefied olefin itself that can be supplied to the polymerization is used as a solvent.

[0157] The polymerization conditions are such that the transition metal complex (A) is usually 10 -12 ~10 -1 mol, preferably 10 -8 ~10 -2 mol per liter of the reaction volume. The polymerization temperature is usually in the range of -50 to 200 °C, preferably 0 to 170 °C, more preferably 30 to 170 °C. The polymerization pressure is usually under normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch, semi-continuous, and continuous methods. Furthermore, it can also be carried out as a multi-stage reaction under two or more conditions with different reaction conditions.

[0158] The molecular weight of the obtained ethylene-based polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. In particular, hydrogen can sometimes obtain the effects of improving the polymerization activity of the catalyst and increasing or decreasing the molecular weight of the polymer, and can be said to be a preferred additive. When hydrogen is added to the system, the appropriate amount is about 0.00001 to 100 NL per mole of olefin. The hydrogen concentration in the system can be adjusted not only by adjusting the supply amount of hydrogen, but also by carrying out a reaction that generates or consumes hydrogen in the system, a method of separating hydrogen using a membrane, or discharging a part of the gas containing hydrogen out of the system.

[0159] The weight average molecular weight (Mw) of the resulting ethylene polymer is preferably 80,000 g / mol or more, more preferably 100,000 g / mol or more, still more preferably 120,000 g / mol or more, and particularly preferably 140,000 g / mol or more. The upper limit is not particularly limited, and may be, for example, 1,000,000 g / mol or less. The weight average molecular weight (Mw) of the ethylene polymer is determined by gel permeation chromatography (GPC). Specifically, it can be determined by the method described in the examples.

[0160] Furthermore, in the polymerization system, the above component (G) can be made to coexist for the purpose of suppressing fouling in the polymerization vessel or improving the particle properties by electrostatic adhesion of the catalyst or the polymer. With respect to the olefin polymer obtained by the production method of the present invention, after synthesis by the above method, post-treatment steps such as a known catalyst deactivation treatment step, a catalyst residue removal step, and a drying step may be performed as necessary.

[0161] In order to suppress variations in physical property values, the olefin polymer particles obtained by the polymerization reaction and other components added as desired are melted by an arbitrary method and subjected to kneading, granulation, etc.

Examples

[0162] Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples at all.

[0163] <Evaluation method> 〔Presence or absence of fouling after prepolymerization〕 Regarding the presence or absence of fouling after prepolymerization, it was evaluated by visually observing the deposits on the reactor wall and the stirring blades after the preparation of the prepolymerization catalyst.

[0164] 〔Weight average molecular weight (Mw) of the polymer〕 The weight average molecular weight (Mw) of the ethylene polymer was determined by gel permeation chromatography (GPC). It was calculated from the molecular weight distribution curve obtained by a gel permeation chromatograph (high-temperature size exclusion chromatograph) "Alliance GPC 2000" manufactured by Waters Corporation, and the operating conditions are as follows: <Apparatus and Conditions Used> Measuring apparatus; Gel permeation chromatograph, allianceGPC2000 type (Waters Corporation) Analysis software; Chromatography Data System Empower (trademark, Waters Corporation) Columns; TSKgel GMH6-HT × 2 + TSKgel GMH6-HT × 2 (inner diameter 7.5 mm × length 30 cm, Tosoh Corporation) Mobile phase; o-dichlorobenzene [=ODCB] (special grade reagent, FUJIFILM Wako Pure Chemical Corporation) Detector; Differential refractometer (built into the apparatus) Column temperature; 140 °C Flow rate; 1.0 mL / min Injection volume; 400 μL Sampling time interval; 1 second Sample concentration; 0.15% (w / v) Molecular weight calibration; Monodisperse polystyrene (Tosoh Corporation) / Molecular weight from 495 to 20.6 million

[0165] [Example 1] <Preparation of Solid Catalyst Slurry> In a reactor with a stirrer having an internal volume of 270 L, under a nitrogen atmosphere, silica gel (manufactured by Fuji Silysia Chemical Ltd.: average particle diameter 70 μm, specific surface area 340 m 2 / g, pore volume 1.3 cm 310 kg (dried at 250 °C for 10 h) was suspended in 77 L of toluene and then cooled to 0 - 5 °C. To this suspension, 19.4 L of a toluene solution of methylaluminoxane (3.5 mmol / mL in terms of Al atoms) was added dropwise over 30 minutes. During this time, the temperature inside the system was maintained at 0 - 5 °C. Subsequently, after contacting at 0 - 5 °C for 30 minutes, the temperature inside the system was raised to 95 °C over about 1.5 hours and then contacted at 95 °C for 4 hours. Then, the temperature was lowered to room temperature, the supernatant was removed by decantation, and after further washing twice with toluene, a toluene slurry with a total volume of 115 L was prepared. When a part of the obtained slurry component was sampled and its concentration was examined, the slurry concentration was 270.0 g / L and the Al concentration was 1.322 mol / L.

[0166] 37.5 mL of toluene and 230.0 mL of the toluene slurry obtained above (solid content = 62.1 g, Al = 304.08 mmol) were charged into a 1 L reactor with a stirrer that had been sufficiently purged with nitrogen. Next, 200 mL of a toluene solution was added to a concentration of 0.0076 mol / L of dimethylsilylene(2 - indenyl)(4 - (3,5 - di - tert - butyl - 4 - methoxyphenyl)-7 - methoxy - 1 - indenyl)zirconium dichloride [synthesized by the method described in JP - A - 2019 - 059933], and after contacting at a system temperature of 20 - 25 °C for 1 hour, the supernatant was removed by decantation, and after further washing twice with hexane, a solid catalyst slurry with a total volume of 410 mL was prepared. When a part of the obtained slurry component was sampled and its concentration was examined, the slurry concentration was 154.0 g / L and the Al concentration was 0.742 mol / L.

[0167] <Preparation of prepolymerization catalyst> Into a 1 L stainless steel reactor with a stirrer, which had been fully purged with nitrogen, 228.6 mL of hexane and 75.0 mL of the above solid catalyst slurry (11.6 g as solid content) were charged. Next, diisobutylaluminum hydride was added so that the concentration of organoaluminum in the solvent in the system became 1.1 mmol / L. 15 g of ethylene was supplied at a rate of 3.3 L / hr per 1 g of the solid catalyst component. The temperature in the system was controlled at 25 °C while ethylene supply was stopped after charging diisobutylaluminum hydride. No deposits were observed on the reactor wall and the stirring blades after the preparation of the prepolymerization catalyst. The entire amount of the obtained slurry was charged into a 1 L glass filter that had been fully purged with nitrogen under a nitrogen atmosphere, and then the pressure was reduced to -68 kPaG over about 1 hour. When -68 kPaG was reached, vacuum drying was carried out for about 2 hours to obtain a prepolymerization catalyst. Also, the fluidity of the obtained prepolymerization catalyst was good.

[0168] <Production of Ethylene Polymer> 500 mL of heptane was charged into a 1 L stainless steel autoclave that had been fully purged with nitrogen. After replacing the inside of the system with ethylene, 3 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 1.00 g of the prepolymerization catalyst prepared above were charged, and the temperature in the system was raised to 80 °C. Next, a polymerization reaction was carried out for 90 minutes under the conditions of a total pressure of 0.8 MPaG and 80 °C by continuously introducing ethylene. The polymer was recovered by filtration and dried under reduced pressure at 80 °C overnight to obtain 125.8 g of an ethylene polymer. The productivity (the amount of ethylene polymer produced per 1 g of the solid catalyst component) was 1,840 g, and the weight average molecular weight was 143,000 g / mol.

[0169] [Example 2], [Comparative Example 1] - [Comparative Example 4] In the preparation of the prepolymerization catalyst of Example 1, the same procedure was carried out except that the ethylene supply amount, the ethylene supply rate, and the temperature in the system were changed as shown in Table 8. For Comparative Example 2, since fouling was observed on the reactor wall and the stirring blades after the preparation of the prepolymerization catalyst, the production of the ethylene polymer was not carried out. The results are shown in Table 8.

[0170]

Table 8

Claims

1. A method for producing a prepolymerization catalyst (X) for olefin polymerization, comprising a step of prepolymerizing a solid catalyst component (Sa) containing a transition metal complex (A) and a solid carrier (S) under the conditions that the concentration of the organoaluminum compound excluding the solid content in the solvent is 0.1 mmol / L or more and 10 mmol / L or less, and the prepolymerization temperature is 10 to 30°C, and an olefin having 2 or more carbon atoms is supplied to 1 g of the solid catalyst component (Sa) at a rate of 1 to 10 L / hr.

2. The method for producing a prepolymerization catalyst (X) according to claim 1, wherein the prepolymerization amount of the olefin having 2 or more carbon atoms is 1 g or more and 50 g or less per 1 g of the solid catalyst component (Sa).

3. The method for producing a prepolymerization catalyst (X) according to claim 1, wherein the transition metal complex (A) contains a Group 4 transition metal atom of the periodic table, and the solid carrier (S) is a porous oxide.

4. The method for producing a prepolymerization catalyst (X) according to claim 1, wherein the prepolymerization catalyst (X) contains an organoaluminum oxy compound (B-2).

5. The method for producing a prepolymerization catalyst (X) according to claim 1, wherein the transition metal complex (A) is represented by the following general formula [1]. (In general formula [1], M is a Group 4 transition metal atom of the periodic table, 【Chemical 1】 n is an integer of 1 to 4 selected so that the transition metal complex (A) is electrically neutral, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone pair of electrons. 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-based derivative group. When n is 2 or more, the groups represented by a plurality of Xs may be the same or different from each other, and may be bonded to each other to form a ring, Q is a Group 14 atom of the periodic table,

6. 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 to R ６ Among them, adjacent substituents may combine with each other to form a ring which may have a substituent. R ７ ~R １２ Among adjacent substituents of R ７ to R １２ , they may combine with each other to form a ring which may have a substituent. R １３ and R １４ may be joined to each other to form a ring containing Q, and this ring may have a substituent. A method for producing an olefin polymer, characterized in that olefin is polymerized or copolymerized in the presence of the prepolymerization catalyst (X) according to any one of claims 1 to 5. ​

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