Olefin polymerization catalyst and method for producing an ethylene-based polymer using the same

Abstract

To provide an olefin polymerization catalyst that makes it possible to produce with high production efficiency a low-density ethylenic polymer which has many long chain branching and is excellent in moldability and mechanical strength.SOLUTION: The olefin polymerization catalyst comprises compounds represented by formulas (1) and (2).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a catalyst for olefin polymerization and a method for producing an ethylene-based polymer using the catalyst. More specifically, the present invention relates to a catalyst for olefin polymerization capable of stably producing an ethylene-based polymer having many long-chain branches and excellent in moldability and mechanical strength, and a method for producing an ethylene-based polymer using the catalyst.

Background Art

[0002] It is well known that ethylene-based polymers obtained with Ziegler catalysts or metallocene catalysts generally have low melt tension and tend to be inferior in moldability to high-pressure low-density polyethylene. To solve this problem, methods such as blending high-pressure low-density polyethylene with an ethylene-based polymer obtained using a Ziegler catalyst or a metallocene catalyst (for example, Patent Document 1), or producing a long-chain branched ethylene-based polymer using a specific metallocene catalyst (for example, Patent Document 2) have been disclosed.

[0003] In addition, it has been reported that by using two specific crosslinked metallocene compounds, a large number of long-chain branches can be introduced to produce an ethylene-based polymer excellent in moldability (for example, Patent Documents 3 and 4).

[0004] In addition, methods for producing long-chain branched ethylene-based polymers using two metallocene compounds have also been reported in Patent Documents 5 to 8.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

[0006] In the methods of Patent Documents 1 to 8 described above, when attempting to produce a target low-density long-chain branched ethylene-based polymer, a problem has been found in that the amount of comonomer added is large and the production efficiency is not necessarily sufficient.

[0007] The present invention has been made in view of the above-described new problems, and an object thereof is to provide a catalyst for olefin polymerization capable of producing a low-density ethylene-based polymer having many long-chain branches and excellent in molding processability and mechanical strength with high production efficiency, and a method for producing an ethylene-based polymer using the catalyst. [Means for Solving the Problems]

[0008] As a result of intensive studies in view of the above situation, the present inventors have found that by using two crosslinked metallocene compounds having a specific structure in the same polymerization system, a low-density ethylene-based polymer having many long-chain branches and excellent in molding processability and mechanical strength can be produced with high production efficiency, and have completed the present invention.

[0009] That is, the catalyst for olefin polymerization of the present invention comprises the following component (A), the following component (B), the following component (C), and a solid carrier (S). Component (A): A transition metal compound represented by the following general formula (1);

[0010] [Chemical formula] [In 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 compound [A] is electrically neutral, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating 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 derivative group. When n is 2 or more, the groups represented by 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. Q 1 is an atom of Group 14 of the periodic table, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 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 8 is a hydrogen atom, a methyl group, an ethyl group, an aromatic hydrocarbon group or an aromatic hetero five-membered ring group. R 1 ~R 6 Among the adjacent substituents, they may be bonded to each other to form a ring which may have a substituent. R 7 ~R 12 Among the adjacent substituents, 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 1 , and this ring may have a substituent.] Component (B): A transition metal compound represented by the following general formula (2);

[0011] [Chemical formula] [In formula (2), M is a Group 4 transition metal atom of the periodic table, X is each independently an atom or group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, and a phosphorus-containing group, Q 2 is a group selected from hydrocarbon groups having 1 to 20 carbon atoms, halogen-containing groups, silicon-containing groups, germanium-containing groups, and tin-containing groups, R 15 ~R 26 are each independently selected from a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, and two adjacent groups may be linked to form a ring.] Component (C): At least one compound selected from the group consisting of an organometallic compound (c-1) represented by the following general formulas (3) to (5), an organoaluminum oxy compound (c-2), and a compound (c-3) that reacts with Component (A) and Component (B) to form an ion pair; R a m Al(OR b ) n H p X q ···(3) [In formula (3), R a and R b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, X represents a halogen atom, m is a number where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 0 ≦ q < 3, and m + n + p + q = 3.] M a AlR a 4···(4) [In formula (4), M a represents Li, Na, or K, and R arepresents a hydrocarbon group having 1 to 15 carbon atoms. R a r M b R b s X t ···(5) [In formula (5), R a and R b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, M b is selected from Mg, Zn, and 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.

[0012] In addition, the method for producing an ethylene-based polymer of the present invention is characterized in that ethylene is polymerized alone or ethylene is copolymerized with an olefin having 3 to 20 carbon atoms in the presence of the olefin polymerization catalyst of the present invention.

[0013] The ethylene-based polymer obtained by the production method of the present invention is preferably a copolymer of ethylene and an α-olefin having 4 to 20 carbon atoms and satisfies the following requirements (1) to (4). (1) The melt flow rate (MFR) at 2.16 kg load at 190 °C is 0.1 g / 10 min or more and 30 g / 10 min or less; (2) The density is 875 kg / m 3 or more and 945 kg / m 3 or less; (3) The ratio of the zero-shear viscosity [η0(P)] at 200 °C to the 6.8th power (Mw 6.8 ) of the weight-average molecular weight measured by the GPC-viscosity detector method (GPC-VISCO) (η0 / Mw 6.8 ) is 0.03 × 10 -30 or more and 7.5 × 10 -30 or less; (4) The ratio of the intrinsic viscosity [[η]](dl / g) measured in decalin at 135 °C to the 0.776th power (Mw 0.776 ) of the weight-average molecular weight measured by the GPC-viscosity detector method (GPC-VISCO) ([[η]] / Mw 0.776 ) is 0.90 × 10-4 is 1.65×10 -4 or less.

Advantages of the Invention

[0014] By using the olefin polymerization catalyst of the present invention, a low-density ethylene polymer having many long-chain branches and excellent moldability and mechanical strength can be produced with high production efficiency.

Best Mode for Carrying Out the Invention

[0015] Hereinafter, the olefin polymerization catalyst according to the present invention and the method for producing an ethylene polymer using the catalyst will be described in detail. In the present invention, the term "polymerization" may be used in a meaning including not only homopolymerization but also copolymerization, and the term "polymer" may be used in a meaning including not only homopolymers but also copolymers.

[0016] [Olefin Polymerization Catalyst] The olefin polymerization catalyst of the present invention comprises a component (A), a component (B), a component (C) and a solid carrier (S) described below.

[0017] <Component (A)> Component (A) is a transition metal compound represented by the following general formula (1) (hereinafter also referred to as "transition metal compound (1)"). The olefin polymerization catalyst of the present invention contains at least one kind of transition metal compound (1). That is, as component (A), a plurality of kinds of transition metal compounds (1) may be used.

[0018]

Chemical formula

[0019] In the formula (1), n is an integer of 1 to 4 that satisfies the valence of M, preferably 2. In the formula (1), 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 derivative group; when n is 2 or more, a plurality of Xs may be the same or different from each other, and may be bonded to each other to form a ring. X is preferably a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an oxygen-containing group, more preferably a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0020] Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and chlorine is particularly preferred.

[0021] Examples of the hydrocarbon group having 1 to 20 carbon atoms include linear or branched alkyl groups such as methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group (butan-2-yl group), tert-butyl group (2-methylpropane-2-yl group), iso-butyl group (2-methylpropyl group), pentan-2-yl group, 2-methylbutyl group, iso-pentyl group (3-methylbutyl group), neopentyl group (2,2-dimethylpropyl group), siamyl group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group (2,3-dimethylbutan-2-yl group), 4,4-dimethylpentyl group; Linear or branched alkenyl groups or unsaturated double bond-containing groups such as 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); Linear or branched alkynyl groups or unsaturated triple bond-containing groups such as ethynyl group, prop-2-yn-1-yl group, propargyl group (prop-1-yn-1-yl group); Aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups such as benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-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); Cyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norbornenyl group, 1-adamantyl group, 2-adamantyl group; 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, ter-phenyl group, binaphthyl group, acenaphthylenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group, etc. may be mentioned.

[0022] Among the hydrocarbon groups, a methyl group, iso-butyl group, neopentyl group, silyl group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group are preferable.

[0023] 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. Among the halogen-containing groups, a pentafluorophenyl group is preferable.

[0024] 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. Among the silicon-containing groups, a trimethylsilylmethyl group is preferable.

[0025] 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. Among these oxygen-containing groups, a methoxy group, an ethoxy group, an iso-propoxy group, and a tert-butoxy group are preferable.

[0026] 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). Among these sulfur-containing groups, a triflate (trifluoromethanesulfonate) is preferable.

[0027] 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. Among these nitrogen-containing groups, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a pyrrolyl group, and a bistriflylimide group are preferable.

[0028] Examples of the phosphorus-containing group include a hexafluorophosphate anion. 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

[0029]

Chemical formula

[0030] 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, and the like.

[0031] 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.

[0032] In the formula (1), Q 1is a Group 14 transition atom in the periodic table, specifically a carbon atom, a silicon atom, a germanium atom or a tin atom, preferably a carbon atom or a silicon atom, and particularly preferably a silicon atom.

[0033] In the formula (1), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、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, and R 8 is a hydrogen atom, a methyl group, an ethyl group, an aromatic hydrocarbon group or an aromatic heterocyclic five-membered group.

[0034] R 1 ~R 7 and R 9 ~R 14 The hydrocarbon group having 1 to 40 carbon atoms as R

[0035] The hydrocarbon group having 1 to 40 carbon atoms includes, for example, Linear or branched alkyl groups 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), siamil 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; Alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms in a linear or branched form, such as vinyl group, allyl group, propenyl group, iso-propenyl group, arylenyl group, but-3-en-1-yl group, crotyl group, but-3-en-2-yl group, methallyl group, pent-4-en-1-yl group, pent-3-en-1-yl group, pent-2-en-1-yl group, iso-pentenyl group, 2-methylbut-3-en-1-yl group, pent-4-en-2-yl group, prenyl group, 2-methyl-but-2-en-1-yl group, pent-3-en-2-yl group, 2-methyl-but-3-en-2-yl group, pent-1-en-3-yl group, pent-2,4-dien-1-yl group, pent-1,3-dien-1-yl group, pent-1,4-dien-3-yl group, iso-prenyl group (2-methyl-but-1,3-dien-1-yl group), pent-2,4-dien-2-yl group, hex-5-en-1-yl group, hex-4-en-1-yl group, hex-3-en-1-yl group, hex-2-en-1-yl group, 4-methyl-pent-4-en-1-yl group, 3-methyl-pent-4-en-1-yl group, 2-methyl-pent-4-en-1-yl group, hex-5-en-2-yl group, 4-methyl-pent-3-en-1-yl group, 3-methyl-pent-3-en-1-yl group, 2,3-dimethyl-but-2-en-1-yl group, 2-methylpent-4-en-2-yl group, 3-ethylpent-1-en-3-yl group, hex-3,5-dien-1-yl group, hex-2,4-dien-1-yl group, 4-methylpent-1,3-dien-1-yl group, 2,3-dimethyl-but-1,3-dien-1-yl group, hex-1,3,5-trien-1-yl group, 2-(cyclopentadienyl)propan-2-yl group, 2-(cyclopentadienyl)ethyl group; 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 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 hydrocarbon groups 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, 3,5-di-tert-butyl-4-methoxyphenyl group, allylphenyl group, (but-3-en-1-yl)phenyl group, (but-2-en-1-yl)phenyl group, methallylphenyl group, prenylphenyl group, 4-adamantylphenyl group, 3,5-di-adamantylphenyl group, naphthyl group, biphenyl group, tert-phenyl group, binaphthyl group, acenaphthylenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group and the like.

[0036] 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.As the hydrocarbon group having 1 to 20 carbon atoms, 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 (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, 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), but-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), ethynyl group, prop-2-yn-1-yl group, propargyl group (prop-1-yn-1-yl group), 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), cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norbornenyl group, 1-adamantyl group, 2-adamantyl group may be mentioned.

[0037] As the aromatic hydrocarbon group having 6 to 40 carbon atoms, preferably, a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 2,6-di-iso-propylphenyl group, a 2,4,6-tri-iso-propylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, a 3,5-di-tert-butyl-4-methoxyphenyl group, an allylphenyl group, a prenylphenyl group, a 4-adamantylphenyl group, a naphthyl group, a biphenyl group, a ter-phenyl group, a binaphthyl group, a phenanthryl group, an anthracenyl group, a ferrocenyl group can be mentioned.

[0038] R 1 ~R 7 and R 9 ~R 14Examples of the halogen-containing group as such 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.

[0039] Among the halogen-containing groups, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a trifluoromethoxyphenyl group, a pentafluorobiphenyl group, a trifluoromethylbiphenyl group, a bistrifluoromethylbiphenyl group, a trifluoromethoxy group, a pentafluorophenoxy group, a bistrifluoromethylphenoxy group, a bistrifluoromethylphenoxy group, a difluoromethylenedioxyphenyl group, 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.

[0040] R 1 ~R 7 and R 9 ~R 14Examples of the silicon-containing group as such 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 indenylmethylsilyl 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.

[0041] Among these silicon-containing groups, a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, a cyclopentadienyldimethylsilyl group, a cyclopentadienyldiphenylsilyl group, an indenylmethylsilyl group, an indenylmethylsilyl group, a fluorenyldimethylsilyl group, a fluorenyldiphenylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-iso-propylsilylphenyl group, a 4-triphenylsilylphenyl group, a 3,5-bis(trimethylsilyl)phenyl group, and the like are preferable, and a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-iso-propylsilylphenyl group, a 3,5-bis(trimethylsilyl)phenyl group are more preferable.

[0042] R 1 ~R 7 and R 9 ~R 14Examples of the oxygen-containing group as such 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, and the like.

[0043] 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.

[0044] R 1 ~R 7 and R 9 ~R 14Examples of the nitrogen-containing group as such 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, isoquinolyl group, tetrahydro-isoquinolyl 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.

[0045] 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, tetramethyldi julolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, isoquinolyl group, tetrahydro-isoquinolyl 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, tetramethyldi julolidinyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group, imidazolyl group are more preferable.

[0046] R 1 ~R 7 and R 9 ~R 14Examples of the sulfur-containing group as such 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.

[0047] 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.

[0048] R 8 The aromatic group as such may have a substituent, and specifically, the above-described R 1 ~R 7 and R 9 ~R 14 Examples of the aromatic hydrocarbon group having 6 to 40 carbon atoms, which was given as an example of the hydrocarbon group having 1 to 40 carbon atoms as such, include.

[0049] R 8 The heterocyclic aromatic group as such may have a substituent, and examples thereof include groups represented by the following general formulas [5a] to [5h].

[0050]

Chem.

[0051] Examples of the hydrocarbon group having 1 to 20 carbon atoms in the above R d include the above-mentioned R 1 ~R 7 and R 9 ~R 14Among the examples of the hydrocarbon group having 1 to 40 carbon atoms cited as such, those having 1 to 20 carbon atoms are cited. 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, ter-phenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrocenyl group are cited. 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, ter-phenyl group are cited.

[0052] R d is adjacent R dThey may combine with each other to form a saturated or unsaturated hydrocarbon group having 5 to 8 members which may have a substituent and is independently condensed with a complex 5-membered ring portion. Although not particularly limited as long as the effects of the present invention are achieved, it is preferably a 5- or 6-membered ring. In this case, as a structure combined with the aromatic ring portion of the mother 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 and the like can be mentioned.

[0053] Among the heterocyclic aromatic groups represented by the above formulas [5a] to [5h], the heterocyclic aromatic group represented by the above formula [5a] is preferable. Among the heterocyclic aromatic groups represented by the above formula [5a], a 2-furyl group, a 5-methyl-2-furyl group, a 2-thienyl group, and a 5-methyl-2-thienyl group are preferable.

[0054] In the above formula (1), R 1 ~R 6 Among the adjacent substituents (for example, R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , and R 5 and R 6 ), they may combine with each other to form a ring which may have a substituent. As the ring formed in this case, a 5- to 8-membered ring composed of a saturated hydrocarbon (excluding the hydrocarbon of the indenyl ring portion) or an unsaturated hydrocarbon which is condensed with an indenyl ring portion and may have a substituent is preferable. When there are a plurality of rings, these may be the same as or different from each other. Although not particularly limited as long as the effects of the present invention are achieved, the ring is more preferably a 5- or 6-membered ring. In this case, as a structure combined with the above ring and the indenyl ring portion of the mother nucleus, for example, a substituted benzoindenyl ring, a substituted tetrahydroindacene ring, and a substituted cyclopentatetrahydronaphthalene can be mentioned, and a substituted benzoindenyl ring and a substituted tetrahydroindacene ring are preferable.

[0055] In the formula (1), R 7 ~R 12 Among them, adjacent substituents (e.g., R 7 and R 8 , R 8 and R 9 , R 9 and R 10 , R 10 and R 11 , and R 11 and R 12 ) may be bonded to each other to form a ring which may have a substituent. 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 part) or an unsaturated hydrocarbon which may have a substituent and is fused to the indenyl ring part. When there are a plurality of rings, these may be the same as or different from each other. Although not particularly limited as long as the effects of the present invention are achieved, the ring is more preferably a 5- or 6-membered ring. In this case, examples of the structure combining the ring and the indenyl ring part 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, and a substituted benzoindenyl ring and a substituted tetrahydroindacene ring are preferred.

[0056] In the formula (1), R 13 and R 14 may be bonded to each other to form a ring containing Q 1 , and these rings may have a substituent. The ring formed in this case preferably forms 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, it is preferably a 4- to 6-membered ring. In this case, examples of the structure combined with Q 1 include 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), and a substituted silafluorene ring, and a substituted cyclopentane ring, a substituted silacyclobutane ring, and a substituted silacyclopentane ring are preferred.

[0057] As a preferred embodiment of the transition metal compound (1), in the formula (1), M is a zirconium atom or a hafnium atom, X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or an oxygen-containing group, and Q 1 is a carbon atom or a silicon atom, and R 1 ~R 6 and R 9 ~R 14 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, and R 7 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an aromatic heterocyclic five-membered ring group containing at least one atom selected from the group consisting of nitrogen, oxygen and sulfur (Embodiment 1-a). As a more preferred embodiment, in the above Embodiment 1-a, Q 1 is a silicon atom, R 1 , R 6 and R 8 are hydrogen atoms, and R 2 ~R 5 and R 9 ~R 14 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group or a nitrogen-containing group (Embodiment 1-b). As an even more preferred embodiment, in the above Embodiment 1-b, R 9 is an aromatic hydrocarbon group having 6 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group or a nitrogen-containing group (Embodiment 1-c).

[0058] Specific examples of the transition metal compound (1) are shown below, but the scope of the present invention is not particularly limited thereby. For convenience, the ligand structure excluding the part represented by MXn (metal part) of the transition metal compound (1) is a 2-indenyl ring part, a 1-indenyl ring part, an indenyl ring part R 1 , R 6 and R 8 substituents, an indenyl ring part R 2 , R5 , R 9 and R 12 substituents, indenyl ring moiety R 3 , R 4 , R 10 and R 11 substituents, 1-indenyl ring moiety R 7 substituents, divide the structure of the bridging moiety into seven. The abbreviation of the 2-indenyl ring moiety is α, the abbreviation of the 1-indenyl ring moiety is β, and the indenyl ring moiety R 1 , R 6 and R 8 substituents abbreviation is γ, indenyl ring moiety R 2 , R 5 , R 9 and R 12 substituents abbreviation is δ, indenyl ring moiety R 3 , R 4 , R 10 and R 11 substituents abbreviation is ε, 1-indenyl ring moiety R 7 substituents abbreviation is ζ, the abbreviation of the structure of the bridging moiety is η, and the abbreviations of each substituent are shown in [Table 1] to [Table 7].

[0059]

Table 1

[0060]

Table 2

[0061]

Table 3

[0062]

Table 4

[0063]

Table 5

[0064]

Table 6

[0065]

Table 7

[0066] 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.

[0067] According to the above notation, 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 the substituents are the δ-1, 2-indenyl ring moiety R in [Table 4] 3 and R 4 All the substituents are the ε-1, 1-indenyl ring moiety R in [Table 5] 7 The substituent is the ζ-30, 1-indenyl ring moiety R in [Table 6] 9 The substituent is the δ-38, 1-indenyl ring moiety R in [Table 4] 12 When the combination is such that the substituent is the δ-3 in [Table 4] and the bridging moiety is the η-20 in [Table 7], and MXn of the metal moiety is ZrCl2, the compound represented by the following formula [6] is exemplified.

[0068]

Chemical formula

[0069] Also, when the 2-indenyl ring moiety is the α-1 in [Table 1], the 1-indenyl ring moiety is the β-2 in [Table 2], the indenyl ring moieties R 1 , R 6 and R 8 All the substituents are the γ-1, 2-indenyl ring moiety R in [Table 3] 2 and R 5 All the substituents are the δ-2, 2-indenyl ring moiety R in [Table 4] 3 and R 4 All the substituents are the ε-1, 1-indenyl ring moiety R in [Table 5] 7 When the combination is such that the substituent is the ζ-1 in [Table 6] and the bridging moiety is the η-4 in [Table 7], and MXn of the metal moiety is Zr(NMe2)2, the compound represented by the following formula [7] is exemplified.

[0070]

Chemical formula

[0071] Also, when the 2-indenyl ring moiety is the α-3 in [Table 1], the 1-indenyl ring moiety is the β-1, the 2-indenyl ring moieties R 1 and R 6 All the substituents are the γ-2, indenyl ring moiety R in [Table 3] 2 , R5 and R 12 wherein all 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, an example of the compound represented by the following formula [8] is shown.

[0072]

Chemical formula

[0073] Also, when the 2-indenyl ring moiety is α-1 in [Table 1], the 1-indenyl ring moiety is β-1 in [Table 2], and the 2-indenyl ring moiety R 1 and R 6 wherein all 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 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 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), an example of the compound represented by the following formula [9] is shown.

[0074]

Chemical formula

[0075] The substituted indenyl compound as a 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, JP-A 2019-059933, etc.

[0076] Examples of known production methods for the transition metal compound (1) and the precursor compound (ligand) include "Macromolecules 2001, 34, 2072.", "Macromolecules 2003, 36, 9325.", "Organometallics 2004, 23, 5332.", "Eur. J. Inorg. Chem. 2005, 1003.", "Eur. J. Inorg. Chem. 2009, 1759.", etc.

[0077] Further, in the transition metal compound (1), there are two directions in which the planes of the indenyl ring moieties that are bonded to the central metal with the crosslinked moiety in between exist (the front surface and the back surface). Therefore, when there is no plane of symmetry in the 2-indenyl ring moiety, there are, for example, two types of structural isomers represented by the following general formula [10a] or [10b].

[0078] [Chemical formula] Similarly, for the substituent R of the crosslinked portion 13 and R 14 even when they are not the same, there are, for example, two types of structural isomers represented by the following general formula [11a] or [11b].

[0079] [Chemical formula] Purification, separation, or selective production of these structural isomer mixtures can be achieved by known methods, and the production method is not particularly limited. Known production methods include those listed as the production methods of the transition metal compound (1) above, as well as the production methods disclosed in JP-A-10-109996, "Organometallics 1999, 18, 5347.", "Organometallics 2012, 31, 4340.", JP-T-2011-502192, etc.

[0080] Within the range of the transition metal compound (1), the transition metal compound may be used alone, two or more thereof may be used in combination, a structural isomer mixture may be used, a structural isomer may be used alone, or two or more structural isomer mixtures may be used. As described above, according to the present invention, an ethylene polymer having many long-chain branches introduced can be produced with high catalytic activity using only the transition metal compound (1) as the transition metal compound constituting the ethylene polymerization catalyst. However, within the range where this effect is not impaired, one or more transition metal compounds different from the transition metal compound (1) may be used in combination as the transition metal compound. At this time, the transition metal compound (1) may be in any of the above embodiments.

[0081] <Component (B)> Component (B) is a transition metal compound represented by the following general formula (2) (hereinafter also referred to as "transition metal compound (2)"). The olefin polymerization catalyst of the present invention contains at least one kind of transition metal compound (2). That is, as component (B), a plurality of kinds of transition metal compounds (2) may be used.

[0082] [Chem.]

[0083] The definitions of the symbols in formula (2) are as follows. M is a Group 4 transition metal atom of the periodic table, specifically a titanium atom, a zirconium atom, or a hafnium atom, preferably a zirconium atom.

[0084] X is a monovalent atom or group, and each is independently an atom or group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, and a phosphorus-containing group, preferably a halogen atom or a hydrocarbon group. Specific examples of the halogen atom, hydrocarbon group, halogen-containing hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, and phosphorus-containing group are the same as those exemplified in the above formula (1).

[0085] Q 2 is a divalent group that binds two ligands, and is a group selected from a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, preferably a hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group, a substituted alkylene group, and an alkylidene group, and a silicon-containing group, and particularly preferably a hydrocarbon group having 1 to 10 carbon atoms such as an alkylene group, a substituted alkylene group, and an alkylidene group.

[0086] Examples of the hydrocarbon group having 1 to 20 carbon atoms (divalent hydrocarbon group having 1 to 20 carbon atoms) include alkylene groups such as methylene, ethylene, propylene, and butylene; substituted alkylene groups such as isopropylidene, dimethylmethylene, diethylmethylene, dipropylmethylene, diisopropylmethylene, dibutylmethylene, methylethylmethylene, methylbutylmethylene, methyl-t-butylmethylene, dihexylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, ditolylmethylene, methylnaphthylmethylene, dinaphthylmethylene, 1-methylethylene, 1,2-dimethylethylene, and 1-ethyl-2-methylethylene; cycloalkylene groups such as cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo[3.3.1]nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, and dihydroindenylidene; and alkylidene groups such as ethylidene, propylidene, and butylidene.

[0087] Examples of the silicon-containing group (divalent silicon-containing group) include silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, dibutylsilylene, methylbutylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, ditolylsilylene, methylnaphthylsilylene, dinaphthylsilylene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, and cycloheptamethylenesilylene groups, and preferably dimethylsilylene, dibutylsilylene, and diphenylsilylene.

[0088] Examples of the germanium-containing group (divalent germanium-containing group) or the tin-containing group (tin-containing group) include groups obtained by converting silicon to germanium or tin in the above silicon-containing group.

[0089] Examples of the halogen-containing group (divalent halogen-containing group) include groups in which one or more hydrogen atoms in the above-mentioned alkylene group, substituted alkylene group, cycloalkylene group, alkylidene group or silicon-containing group are substituted with appropriate halogen atoms (halogen-containing silicon-containing groups), such as bis(trifluoromethyl)methylene, 4,4,4-trifluorobutylmethylmethylene, bis(trifluoromethyl)silylene, 4,4,4-trifluorobutylmethylsilylene group and the like.

[0090] R 15 ~R 26 are monovalent atoms or groups, each independently selected from a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group and a tin-containing group, and two adjacent groups may be linked to form a ring. Specific examples of the hydrocarbon group, halogen-containing group, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group are the same as those exemplified in the above formula (1). Examples of the germanium-containing group and tin-containing group include groups in which silicon in the silicon-containing group is converted to germanium or tin.

[0091] Specific examples of the transition metal compound (2) include isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconium dichloride, dibutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, dibutylmethylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, dibutylmethylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, dibutylmethylene(cyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconium dichloride, dimethylsilyl(cyclopentadienyl)(fluorenyl)zirconium dichloride, dimethylsilyl(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, dimethylsilyl(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride and dimethylsilyl(cyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconium dichloride. More preferred specific examples include isopropylidene(cyclopentadienyl)(2,7-di-t-butyl-9-fluorenyl)zirconium dichloride, but are not limited thereto.

[0092] The transition metal compound (2) and its production method are not particularly limited as long as the effects of the present invention are achieved. Specific examples thereof include those exemplified in, for example, JP-A-2006-233208.

[0093] In the present invention, the transition metal compound (2) may be used alone, or two or more transition metal compounds having different chemical structures among the transition metal compounds (2) may be used. Further, a structural isomer having the same chemical structure may be used alone, or a mixture of structural isomers having the same chemical structure (for example, a meso form mixture or a racemic form mixture) may be used.

[0094] <Component (C)> Component (C) is at least one compound selected from the group consisting of an organometallic compound (c-1) represented by the following general formulas (3) to (5), an organoaluminum oxy compound (c-2), and a compound (c-3) that reacts with components (A) and (B) to form an ion pair.

[0095] R a m Al(OR b ) n H p X q ···(3) In formula (3), R a and R b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, X represents a halogen atom, m is a number where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 0 ≦ q < 3, and m + n + p + q = 3.

[0096] M a AlR a 4···(4) In formula (4), M a represents Li, Na or K, and R a represents a hydrocarbon group having 1 or more and 15 or less carbon atoms.

[0097] R a r M b R bs X t ···(5) In formula (5), R a and R b each independently represents a hydrocarbon group having 1 to 15 carbon atoms, M b is selected from Mg, Zn, and Cd, X represents a halogen atom, r satisfies 0 < r ≦ 2, s satisfies 0 ≦ s ≦ 1, t satisfies 0 ≦ t ≦ 1, and r + s + t = 2.

[0098] Among the organometallic compounds (c-1), those represented by the formula (3) are preferred. Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tri(2-ethylhexyl)aluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide; alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide; alkylaluminum hydrides such as dimethylaluminum hydride, diethylaluminum hydride, dihydrophenylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diisohexylaluminum hydride, diphenylaluminum hydride, dicyclohexylaluminum hydride, di-sec-heptylaluminum hydride, di-sec-nonylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum methoxide, diisobutylaluminum ethoxide, etc. may be mentioned.

[0099] Examples of the formula (4) include lithium aluminum hydride, etc. Examples of the formula (5) include dialkylzinc compounds described in JP-A-2003-171412, etc., and they can also be used in combination with a phenol compound, etc.

[0100] As the organoaluminum oxy compound (c-2), an organoaluminum oxy compound prepared from trialkylaluminum or tricycloalkylaluminum is preferable, and an aluminoxane prepared from trimethylaluminum or triisobutylaluminum is particularly preferable. Such an organoaluminum oxy compound is used alone or in combination of two or more.

[0101] As the compound (c-3) that reacts with the component (A) and the component (B) to form an ion pair, Lewis acids, ionic compounds, borane compounds, carborane compounds, heteropoly compounds, isopoly compounds, etc. 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 can be used.

[0102] In the olefin polymerization catalyst according to the present invention, when an organoaluminum oxy compound such as methylaluminoxane is used in combination as a cocatalyst component, not only does it exhibit very high polymerization activity with respect to an olefin compound, but it can also react with active hydrogen in a solid carrier to easily prepare a solid carrier component containing the cocatalyst component. Therefore, the component (C) preferably contains at least an organoaluminum oxy compound (c-2).

[0103] <Solid carrier (S)> The solid carrier (S) used in the present invention is an inorganic compound or an organic compound and is a granular or particulate solid.

[0104] Examples of the inorganic compound used as the solid carrier (S) include porous oxides, solid aluminoxane compounds, inorganic chlorides, clays, clay minerals, or ion-exchangeable layered compounds.

[0105] Examples of the porous oxide include SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, and ThO2, or composites or mixtures containing these, specifically, natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, and SiO2-TiO2-MgO. Among these, those with SiO2 as the main component are preferred.

[0106] Note that the porous oxide 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, and Li2O.

[0107] Although the properties of such porous oxides vary depending on their type and production method, as the solid support (S) used in the present invention, the particle size is usually 0.2 to 300 μm, preferably 1 to 200 μm, and the specific surface area is usually 50 to 1200 m 2 / g, preferably 100 to 1000 m 2 / g, and the pore volume is preferably in the range of 0.3 to 30 cm 3 / g. Such a support is used after being calcined, for example, at 100 to 1000 °C, preferably 150 to 700 °C, if necessary.

[0108] Examples of the solid aluminoxane compound include aluminoxanes having a structure represented by the following general formula (S-a), aluminoxanes having a structure represented by the following general formula (S-b), and aluminoxanes having a structure composed of a repeating unit represented by the following general formula (S-c) and a repeating unit represented by the following general formula (S-d).

[0109]

Chemical formula

[0110] In the above formulas (S-a) and (S-b), r represents an integer of 2 to 500, preferably 6 to 300, and particularly preferably 10 to 100. In the above formulas (S-c) and (S-d), s and t each represent an integer of 1 or more. r, s, and t are selected so that the aluminoxane can substantially maintain a solid state under the reaction environment in which it is used.

[0111] Unlike conventional carriers for olefin polymerization catalysts, the solid aluminoxane compound does not contain inorganic solid components such as silica and alumina, and organic polymer components such as polyethylene and polystyrene, and is solidified mainly with an alkylaluminum compound. "Solid state" means that the aluminoxane component substantially maintains a solid state under the reaction environment in which it is used. More specifically, when preparing an olefin polymerization catalyst (e.g., an ethylene polymerization catalyst) by contacting the transition metal compound [A] with the aluminoxane component as described later, and when performing the polymerization of an olefin (e.g., ethylene) (for example, suspension polymerization) using the prepared olefin polymerization catalyst, the aluminoxane component substantially maintains a solid state.

[0112] Whether the aluminoxane component is in a solid state can be most simply confirmed visually. However, for example, during polymerization, visual confirmation is often difficult. In such cases, it is possible to judge from, for example, the properties of the polymer powder obtained after polymerization and the state of adhesion to the reactor. Conversely, if the properties of the polymer powder are good and the adhesion to the reactor is small, even if a part of the aluminoxane component elutes to some extent under the polymerization environment, it does not depart from the gist of the present invention. As indicators for judging the properties of the polymer powder, there are bulk density, particle shape, surface shape, the degree of existence of amorphous polymer, etc. From the viewpoint of quantification, polymer bulk density is preferable. The bulk density is usually in the range of 0.01 to 0.9, preferably 0.05 to 0.6, more preferably 0.1 to 0.5.

[0113] The dissolution ratio of the solid aluminoxane compound in n-hexane maintained at a temperature of 25 °C is usually in the range of 0 to 40 mol%, preferably 0 to 20 mol%, particularly preferably 0 to 10 mol%.

[0114] The dissolution ratio is determined by adding 2 g of the solid aluminoxane compound carrier to 50 ml of n-hexane maintained at 25 °C, stirring for 2 hours, then separating the solution part using a G-4 glass filter, and measuring the aluminum concentration in this filtrate. Therefore, the dissolution ratio is determined as the ratio of the aluminum atoms present in the filtrate to the amount of aluminum atoms corresponding to 2 g of the aluminoxane used.

[0115] As the solid aluminoxane compound, known solid aluminoxanes can be used without limitation. For example, the solid polyaluminoxane composition described in International Publication No. 2014 / 123212 can also be used. Known production methods include, for example, those described in Japanese Examined Patent Publication No. 7-42301, Japanese Unexamined Patent Application Publication No. 6-220126, Japanese Unexamined Patent Application Publication No. 6-220128, Japanese Unexamined Patent Application Publication No. 11-140113, Japanese Unexamined Patent Application Publication No. 11-310607, Japanese Unexamined Patent Application Publication No. 2000-38410, Japanese Unexamined Patent Application Publication No. 2000-95810, International Publication No. 2010 / 55652, and the like.

[0116] The average particle diameter of the solid aluminoxane compound is generally in the range of 0.01 to 50000 μm, preferably 0.1 to 1000 μm, and particularly preferably 1 to 200 μm. The average particle diameter of the solid aluminoxane compound is determined by observing the particles with a scanning electron microscope, measuring the particle diameters of 100 or more particles, and performing weight averaging. First, the particle diameter d of each particle is measured by sandwiching the particle image with two parallel lines in the horizontal and vertical directions and calculating the length, and is obtained by the following formula.

[0117] Particle diameter d = ((horizontal length) 2 + (vertical length) 2 ) 0.5 Next, the weight average particle diameter of the solid aluminoxane compound is obtained by the following formula using the particle diameter d obtained above and the number of particles n.

[0118] Average particle diameter = Σnd 4 / Σnd 3 The solid aluminoxane compound has a specific surface area of 50 to 1000 m 2 / g, preferably 100 to 800 m 2 / g, and a pore volume of 0.1 to 2.5 cm 3 / g is desirable.

[0119] Examples of the inorganic halide include MgCl2, MgBr2, MnCl2, MnBr2, etc. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, after dissolving the inorganic halide in a solvent such as alcohol, a precipitate formed into fine particles by a precipitant may also be used.

[0120] Clay is usually composed mainly of clay minerals. 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. Further, as these clays, clay minerals, and ion-exchangeable layered compounds, not limited to naturally occurring ones, synthetic products can also be used.

[0121] Examples of the clay, clay mineral, or ion-exchangeable layered compound include clay, clay mineral, and an ion-crystalline compound having a layered crystal structure such as a hexagonal close-packed type, an antimony type, a CdCl2 type, a CdI2 type, etc.

[0122] Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyromite clay, allophane, hisingerite, pyrophyllite, umo 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.

[0123] Such clays, clay minerals or ion-exchangeable layered compounds preferably have a pore volume of 0.1 cc / g or more with a pore radius of 20 Å or more as measured by the mercury intrusion method, and particularly preferably 0.3 to 5 cc / g. Here, the pore volume is measured by the mercury intrusion method using a mercury porosimeter in the range of a pore radius of 20 to 3×10 4 Å. When a carrier having a pore volume with a pore radius of 20 Å or more smaller than 0.1 cc / g is used, it tends to be difficult to obtain high polymerization activity.

[0124] It is also preferable to subject the clay and clay minerals to chemical treatment. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a treatment affecting the crystal structure of the clay, etc. can be used. Specifically, examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic substance treatment, etc. The 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 the alkali treatment, the crystal structure of the clay is destroyed, resulting in a change in the structure of the clay. Also, in the salt treatment and organic substance treatment, ion complexes, molecular complexes, organic derivatives, etc. can be formed to change the surface area and the interlayer distance.

[0125] 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. Examples of the guest compound for intercalation include cationic inorganic compounds such as TiCl4, ZrCl4, etc., 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 of such metal hydroxide ions include those mentioned above. 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 etc.), colloidal inorganic compounds such as SiO2, etc. can also coexist. Examples of the pillar include oxides formed by heating and dehydrating after intercalating the above metal hydroxide ions between the layers.

[0126] 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.

[0127] Examples of the organic compound used as the solid support (S) include granular or fine particulate solids having a particle size in the range of 10 to 300 μm. Specific examples of the organic compound include polymers mainly composed of olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, polymers or reaction products mainly composed of vinylcyclohexane, styrene, divinylbenzene, and granular or fine particulate solids composed of their modified products. As the solid support (S), porous oxides are preferred from the viewpoint of preventing foreign substances during molding.

[0128] <Method for preparing olefin polymerization catalyst> The olefin polymerization catalyst according to the present invention is one of the preferred embodiments where the solid catalyst component (X) is prepared by adding the component (A), component (B), component (C), and the solid support (S) into an inert hydrocarbon or a polymerization system using an inert hydrocarbon.

[0129] Examples of the solid catalyst component (X) include an olefin polymerization catalyst comprising a solid catalyst component (X-A) formed from a solid carrier (S), component (C), and component (A), and a solid catalyst component (X-B) formed from a solid carrier (S), component (C), and component (B); and an olefin polymerization catalyst comprising a solid catalyst component (X-C) formed from a solid carrier (S), component (A), component (B), and component (C). Among these, the olefin polymerization catalyst comprising the solid catalyst component (X-C) is more preferred.

[0130] The contact order of each component is arbitrary. However, as a preferred method for preparing an olefin polymerization catalyst, for example, (i) A method of preparing the solid catalyst component (X-A) by contacting component (C) with the solid carrier (S) and then contacting component (A), and preparing the solid catalyst component (X-B) by contacting component (C) with the solid carrier (S) and then contacting component (B). (ii) A method of preparing the solid catalyst component (X-A) by mixing and contacting component (A) and component (C) and then contacting the solid carrier (S), and preparing the solid catalyst component (X-B) by mixing and contacting component (B) and component (C) and then contacting the solid carrier (S). (iii) A method of preparing the solid catalyst component (X-A) by contacting component (C) with the solid carrier (S) and then contacting the contact product of component (A) and component (C), and preparing the solid catalyst component (X-B) by contacting component (C) with the solid carrier (S) and then contacting the contact product of component (B) and component (C). (iv) A method of preparing the solid catalyst component (X-A) by contacting component (C) with the solid carrier (S), then contacting component (A), and then further contacting component (C), and preparing the solid catalyst component (X-B) by contacting component (C) with the solid carrier (S), then contacting component (B), and then further contacting component (C). (v) A method of preparing the solid catalyst component (X-C) by contacting the solid carrier (S) with component (C), then contacting component (A), and then contacting component (B). (vi) A method for preparing a solid catalyst component (X-C) by contacting a solid support (S) with a component (C), then contacting with a component (B), and then contacting with a component (A). (vii) A method for preparing a solid catalyst component (X-C) by contacting a solid support (S) with a component (C), and then contacting with a contact mixture of a component (A) and a component (B). (viii) A method for preparing a solid catalyst component (X-C) by contacting a component (A) with a component (B), then contacting with a component (C), and then contacting with a solid support (S). (ix) A method for preparing a solid catalyst component (X-C) by contacting a solid support (S) with a component (C), then further contacting with a component (C), and then contacting with a component (A) and a component (B) in this order. (x) A method for preparing a solid catalyst component (X-C) by contacting a solid support (S) with a component (C), then further contacting with a component (C), and then contacting with a component (B) and a component (A) in this order. (xi) A method for preparing a solid catalyst component (X-C) by contacting a solid support (S) with a component (C), then further contacting with a component (C), and then contacting with a contact mixture of a component (A) and a component (B). (xii) A method for preparing a solid catalyst component (X-C) by contacting a solid support (S) with a component (C), and then contacting with a contact mixture of a component (A), a component (B), and a component (C). (xiii) A method for preparing a solid catalyst component (X-C) by contacting a solid support (S) with a component (C), then contacting with a contact mixture of a component (A) and a component (C), and then contacting with a component (B). (xiv) A method for preparing a solid catalyst component (X-C) by contacting a solid support (S) with a component (C), then contacting with a contact mixture of a component (B) and a component (C), and then contacting with a component (A). (xv) A method for preparing a solid catalyst component (X-C) by contacting a solid support (S) with a component (C), then further contacting with a component (C), and then contacting with a contact mixture of a component (A) and a component (C) and a contact mixture of a component (B) and a component (C) in this order. (xvi) A method for preparing a solid catalyst component (X-C) by contacting a solid support (S) with component (C), then further contacting component (C), and then contacting the contact mixture of component (B) and component (C) and the contact mixture of component (A) and component (C) in this order. (xvii) A method for preparing a solid catalyst component (X-C) by contacting a solid support (S) with component (C), then further contacting component (C), and then contacting the contact mixture of component (A), component (B) and component (C). (xviii) A method for preparing a solid catalyst component (X-C) by premixing a mixture of component (A) and component (C) with a mixture of component (B) and component (C), and then contacting the contact product of the solid support (S) and component (C). (xix) A method for preparing a solid catalyst component (X-C) by premixing a mixture of component (A) and component (C) with a mixture of component (B) and component (C), then contacting the solid support (S) with component (C), and further contacting the contact mixture with component (C). etc.

[0131] When a plurality of component (C) are used, the component (C)s may be the same or different from each other. Among these, particularly preferred contact orders are (xi), (xiii), (xv ), (xvi), (xvii), (xxii), (xxiii) and (xxiv).

[0132] By contacting component (C) with solid carrier (S), component (C) and solid carrier (S) are chemically bonded by the reaction between the reaction sites in component (C) and the reaction sites in solid carrier (S), and a contact product of component (C) and solid carrier (S) is formed. The contact time between component (C) and solid carrier (S) is usually 0 to 20 hours, preferably 0 to 10 hours, and the contact temperature is usually -50 to 200 °C, preferably -20 to 120 °C. If the initial contact between component (C) and solid carrier (S) is carried out abruptly, the solid carrier (S) will collapse due to the exothermic reaction and reaction energy, the morphology of the obtained solid catalyst component (X) will deteriorate, and when this is used in polymerization, continuous operation is often difficult due to poor polymer morphology. Therefore, at the initial stage of the contact between component (C) and solid carrier (S), for the purpose of suppressing the exothermic reaction, it is preferable to carry out the contact at a low temperature of -20 to 30 °C, or to control the exothermic reaction and react at a rate capable of maintaining the initial contact temperature. The same applies when component (C) and solid carrier (S) are contacted and then component (C) is contacted again. The molar ratio of the contact between component (C) and solid carrier (S) (component (C) / solid carrier (S)) can be arbitrarily selected, but the higher the molar ratio, the more the contact amount of component (A) and component (B) can be increased, and the activity of the solid catalyst component (X) can be improved. Specifically, the molar ratio of component (C) to solid carrier (S) [= molar amount of component (C) / molar amount of solid carrier (S)] is preferably 0.2 to 2.0, particularly preferably 0.4 to 2.0.

[0133] Regarding the contact between the contact product of component (C) and the solid carrier (S) and components (A) and (B), the contact time is usually 0 to 5 hours, preferably 0 to 2 hours, and the contact temperature is usually in the range of -50 to 200 °C, preferably -50 to 100 °C. The contact amount of components (A) and (B) with respect to component (C) greatly depends on the type and amount of component (C). In the case of component (c-1), it is used in an amount such that the molar ratio [(c-1) / M] of component (c-1) to all transition metal atoms (M) in components (A) and (B) is usually 0.01 to 100,000, preferably 0.05 to 50,000. In the case of component (c-2), it is used in an amount such that the molar ratio [(c-2) / M] of the aluminum atoms in component (c-2) to all transition metal atoms (M) in components (A) and (B) is usually 10 to 500,000, preferably 20 to 100,000. In the case of component (c-3), it is used in an amount such that the molar ratio [(c-3) / M] of component (c-3) to all transition metal atoms (M) in components (A) and (B) is usually 1 to 10, preferably 1 to 5. Incidentally, the molar ratio of component (C) to all transition metal atoms (M) in components (A) and (B) can be determined by inductively coupled plasma optical emission spectrometry (ICP spectrometry).

[0134] Examples of the solvent used for preparing the solid catalyst component (X) include inactive hydrocarbon solvents. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; and mixtures thereof, etc. can be mentioned.

[0135] In each of the methods showing the above contact order forms, in the steps including the contact of the solid carrier (S) with the component (C), the contact of the solid carrier (S) with the component (A), the contact of the solid carrier (S) with the component (B), and the contact of the solid carrier (S) with the components (A) and (B), at least one compound selected from (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 may coexist as the component (G). By coexisting such a component (G), fouling during the polymerization reaction can be suppressed, and the particle properties of the produced polymer are improved. Among the components (G), (g-1), (g-2), (g-3), and (g-4) are preferred.

[0136] The use ratio of the component (A) and the component (B) can be appropriately determined according to the molecular weight and molecular weight distribution of the polymer to be produced. For the polymerization of olefins, the above solid catalyst component (X) can be used as it is, but it can also be used after prepolymerizing an olefin with this solid catalyst component (X) to form a prepolymerized catalyst component (XP).

[0137] The prepolymerized catalyst component (XP) can usually be prepared by introducing an olefin in an inert hydrocarbon solvent in the presence of the solid catalyst component (X). As the reaction method, any of batch, semi-continuous, and continuous methods can be used. The reaction can also be carried out under reduced pressure, normal pressure, or increased pressure. By this prepolymerization, usually 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g of polymer is produced per 1 g of the solid catalyst component.

[0138] The prepolymerized catalyst component (XP) prepared in an inert hydrocarbon solvent may be separated from the suspension and then suspended again in an inert hydrocarbon, and an olefin may be introduced into the obtained suspension, or an olefin may be introduced after drying.

[0139] The prepolymerization temperature is usually -20 to 80°C, preferably 0 to 60°C. The prepolymerization time is usually 0.5 to 100 hours, preferably 1 to 50 hours. As the form of the solid catalyst component (X) used in the prepolymerization, those already described can be used without limitation. Further, component (C) is used as necessary, and in particular, the organoaluminum compound represented by the above formula (3) in (c-1) is preferably used. When the organoaluminum compound of formula (3) is used as component (C), the molar ratio of the aluminum atom (Al) in component (C) to the transition metal compounds which are components (A) and (B) (component (C) / transition metal compound) is usually used in an amount of 0.1 to 10,000, preferably 0.5 to 5,000.

[0140] The concentration of the solid catalyst component (X) in the prepolymerization system is desirably usually 1 to 1,000 grams / liter, preferably 10 to 500 grams / liter, in terms of the ratio of the solid catalyst component (X) to 1 liter of the polymerization volume. During prepolymerization, component (G) can be made to coexist for the purpose of suppressing fouling or improving the particle properties.

[0141] Also, for the purpose of improving the fluidity of the prepolymerization catalyst component (XP), heat spot seating during polymerization, and suppressing the generation of polymer lumps, component (G) may be brought into contact with the prepolymerization catalyst component (XP) once generated by prepolymerization. At this time, as component (G) to be used, the above (g-1), (g-2), (g-3), (g-4) are preferred.

[0142] The temperature at the time of mixing and contacting component (G) is usually -50 to 50°C, preferably -20 to 50°C, and the contact time is 1 to 1,000 minutes, preferably 5 to 600 minutes. When mixing and contacting the solid catalyst component (X) and component (G), component (G) is usually used in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.4 to 5 parts by weight, based on 100 parts by weight of the solid catalyst component (X).

[0143] The mixing contact of the solid catalyst component (X) and the component (G) can be carried out in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include the same solvents as those used in the preparation of the solid catalyst component (X).

[0144] The catalyst for olefin polymerization according to the present invention can use the prepolymerization catalyst component (XP) after drying it as a dried prepolymerization catalyst. The drying of the prepolymerization catalyst component (XP) is usually carried out after removing the hydrocarbon as the dispersion medium by filtration or the like from the suspension of the obtained prepolymerization catalyst.

[0145] The drying of the prepolymerization catalyst component (XP) is carried out by maintaining the prepolymerization catalyst component (XP) at a temperature in the range of 70°C or lower, preferably 20 to 50°C, under the flow of an inert gas. It is desirable that the volatile component content of the obtained dried prepolymerization catalyst is 2.0% by weight or less, preferably 1.0% by weight or less. The lower the volatile component content of the dried prepolymerization catalyst, the better. Although there is no particular lower limit, practically it is 0.001% by weight. The drying time is usually 3 to 8 hours depending on the drying temperature. When the volatile component content of the dried prepolymerization catalyst exceeds 2.0% by weight, the fluidity of the dried prepolymerization catalyst may decrease, and it may not be possible to stably supply it to the polymerization reactor.

[0146] Here, the volatile component content of the dried prepolymerization catalyst is measured, for example, by the weight loss method, the method using gas chromatography, or the like. In the weight loss method, the weight loss when the dried prepolymerization catalyst is heated at 110°C for 1 hour in an inert gas atmosphere is determined and expressed as a percentage with respect to the dried prepolymerization catalyst before heating.

[0147] In the method using gas chromatography, volatile components such as hydrocarbons are extracted from the dried prepolymerization catalyst, a calibration curve is created according to the internal standard method, and then it is calculated as % by weight from the GC area.

[0148] When measuring the volatile component content of the dry prepolymerization catalyst, the weight loss method is adopted when the volatile component content of the dry prepolymerization catalyst is about 1% by weight or more, and the method using gas chromatography is adopted when the volatile component content of the dry prepolymerization catalyst is about 1% by weight or less.

[0149] Examples of the inert gas used for drying the prepolymerization catalyst component (XP) include nitrogen gas, argon gas, neon gas, etc. Such an inert gas desirably has an oxygen concentration of 20 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less (volume basis), and a water content of 20 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less (weight basis). If the oxygen concentration and water content in the inert gas exceed the above ranges, the olefin polymerization activity of the dry prepolymerization catalyst may be significantly reduced.

[0150] Since the above dry prepolymerization catalyst has excellent fluidity, it can be stably supplied to the polymerization reactor. In addition, since it is not necessary to entrain the solvent used in suspension in the gas phase polymerization system, polymerization can be carried out stably.

[0151] [Method for producing ethylene-based polymer] Next, the method for producing an ethylene-based polymer according to the present invention will be described. In the presence of the olefin polymerization catalyst of the present invention described above, ethylene is polymerized (homopolymerized or copolymerized) to obtain an ethylene-based polymer. By using the olefin polymerization catalyst of the present invention, a low-density ethylene-based copolymer having high polymerization activity, excellent moldability and mechanical strength, and many long-chain branches can be efficiently produced. The ethylene-based polymer of the present invention refers to those containing 10 mol% or more of ethylene content in the polymer.

[0152] In the present invention, the polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization or gas phase polymerization methods, but in the suspension polymerization method and gas phase polymerization method, it is preferable to use the solid catalyst component (X).

[0153] Specific examples of the inactive hydrocarbon medium used in the liquid phase polymerization method include, for example, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; and mixtures thereof. In the liquid phase polymerization method, olefin itself can also be used as a solvent.

[0154] When ethylene is polymerized using the above catalyst for olefin polymerization, components (A) and (B) are usually in an amount of 10 -12 ~10 -1 mol, preferably 10 -8 ~10 -2 mol per liter of the reaction volume. Further, component (C) is used, and in particular, the organoaluminum compound represented by the formula (3) in (c-1) is preferably used.

[0155] In addition, the polymerization temperature of ethylene using the above solid catalyst component (X) is usually in the range of -50 to +200 °C, preferably 0 to 170 °C, and particularly preferably 60 to 170 °C. The polymerization pressure is usually under normal pressure to 100 kg / cm 2 , preferably normal pressure to 50 kg / cm 2 under the conditions, and the polymerization reaction can be carried out by any of batch, semi-continuous, and continuous methods. Further, the polymerization can also be carried out in two or more stages with different reaction conditions.

[0156] The molecular weight of the obtained polymer can be adjusted by introducing hydrogen into the polymerization system or changing the polymerization temperature. Generally, the more the low molecular weight components, the more likely it is to adhere to the polymerization reactor wall and the stirring blade, which may lead to a decrease in productivity due to the load on the cleaning process. During polymerization, component (G) can be coexisted for the purpose of suppressing fouling or improving the particle properties.

[0157] In the present invention, the olefin supplied to the copolymerization reaction is one or more monomers selected from olefins having 3 to 20 carbon atoms. Specific examples of olefins having 3 to 20 carbon atoms include, for example, α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, and the like. Further, examples of the above olefins include styrene, vinylcyclohexane, dienes, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, and the like; polar monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid, and the like.

[0158] In a preferred embodiment of the present invention, an ethylene-based polymer obtained by copolymerizing ethylene and an α-olefin having 4 to 20 carbon atoms, preferably 6 to 10 carbon atoms, in the presence of the catalyst for olefin polymerization of the present invention preferably satisfies the following requirements (1) to (4). The measurement methods for these requirements are as described in the examples.

[0159] (1) The melt flow rate (MFR) at a load of 2.16 kg at 190 °C is 0.1 g / 10 min or more and 30 g / 10 min or less. The lower limit is preferably 0.5 g / 10 min, more preferably 1.0 g / 10 min, and the upper limit is preferably 25 g / 10 min, more preferably 20 g / 10 min. When the melt flow rate (MFR) is within the above range, the shear viscosity of the ethylene-based polymer is not too high, the moldability is good, and the mechanical strengths such as the tensile strength and heat seal strength of the ethylene-based polymer are good.

[0160] The melt flow rate (MFR) strongly depends on the molecular weight. The smaller the MFR, the larger the molecular weight, and the larger the MFR, the smaller the molecular weight. Also, it is known that the molecular weight of the ethylene polymer is determined by the composition ratio of hydrogen to ethylene (hydrogen / ethylene) in the polymerization system (for example, Kazuo Soga et al., "Catalytic Olefin Polymerization", Kodansha Scientific, 1990, p. 376). Therefore, it is possible to increase or decrease the MFR of the ethylene polymer by increasing or decreasing the hydrogen / ethylene ratio.

[0161] (2) The density is 875 kg / m 3 or more and 965 kg / m 3 or less, preferably 885 kg / m 3 or more and 945 kg / m 3 When the density is within the above range, the film formed from the ethylene polymer has less surface stickiness, excellent antiblocking properties, good impact strength of the film, and good mechanical strengths such as heat seal strength and bag breakage strength.

[0162] Generally, the density depends on the α-olefin content of the ethylene polymer. The lower the α-olefin content, the higher the density, and the higher the α-olefin content, the lower the density. Also, it is known that the α-olefin content in the ethylene polymer is determined by the composition ratio of α-olefin to ethylene (α-olefin / ethylene) in the polymerization system (for example, Walter Kaminsky, Makromol.Chem.193, p. 606 (1992)). Therefore, it is possible to produce an ethylene polymer having a density within the above range by increasing or decreasing the α-olefin / ethylene ratio.

[0163] (3) The ratio of the zero-shear viscosity [η0(P)] at 200 °C to the 6.8th power (Mw 6.8 ) of the weight-average molecular weight measured by the GPC-viscosity detector method (GPC-VISCO) (η0 / Mw 6.8 ) is 0.03 × 10 -307.5×10 or less -30 is as follows. That is, in the ethylene polymer, η0 and Mw satisfy the following formula (Eq-1) 0.03×10 -30 ≦ η0 / Mw 6.8 ≦ 7.5×10 -30 ---(Eq-1) is satisfied. Here, the lower limit is preferably 0.05×10 -30 , more preferably 0.8×10 -30 , and the upper limit is preferably 5.0×10 -30 , more preferably 3.0×10 -30 .

[0164] η0 / Mw 6.8 being 0.03×10 -30 or more and 7.5×10 -30 or less is synonymous with log(η0) and logMw existing in the region defined by the following formula (Eq-1´) when η0 and Mw are plotted on a double logarithmic scale. 6.8Log(Mw)-31.523 ≦ Log(η0) ≦ 6.8Log(Mw)-29.125 --- (Eq-1´)

[0165] When the zero-shear viscosity [η0 (P)] is plotted on a double logarithmic scale against the weight-average molecular weight (Mw), an ethylene polymer that is linear without long-chain branches and whose extensional viscosity does not exhibit strain hardening follows a power law with an exponent of 3.4. On the other hand, an ethylene polymer that has a relatively large number of short long-chain branches and whose extensional viscosity exhibits strain rate hardening is known to exhibit a lower zero-shear viscosity [η0 (P)] than the power law, and its exponent is larger than 3.4 (C Gabriel, H. Munstedt, J. Rheol., 47(3), 619(2003), H. Munstedt, D. Auhl, J. Non-Newtonian Fluid Mech. 128, 62-69, (2005)), and the exponent 6.8 can be empirically selected. The ratio of η0 to Mw 6.8 is also disclosed in JP-A-2011-1545.

[0166] The zero-shear viscosity [η0(P)] of the above ethylene-based polymer at 200 °C is 20 × 10 -13 ×Mw 6.8 In the following cases, the occurrence of take-up surging is suppressed in the ethylene-based polymer.

[0167] Furthermore, when η0 / Mw 6.8 is within the above range, there is an effect that the blocking resistance of the film obtained from the ethylene-based polymer is extremely excellent. The reason for such an effect is presumed as follows.

[0168] It is known that the blocking resistance is remarkably improved by forming minute irregularities on the film surface. When the molten resin flows into the die, extensional stress is generated by the extensional flow. When this extensional stress exceeds the critical value, brittle fracture occurs, and unstable flow at the die exit called melt fracture occurs, and minute irregularities are formed on the surface of the molded body (F.N. Cogswell, Polymer Melt Rheology, Wiley, 1981).

[0169] When η0 / Mw 6.8 is within the claim range, the extensional stress increases at the strain rate in general molding processing, and melt fracture occurs. Due to this melt fracture, minute irregularities are formed on the film surface, so the blocking resistance of the obtained film is extremely excellent.

[0170] It is known that the extensional stress is strongly affected by the number and length of long-chain branches. The more the number, the longer the length, the greater the extensional stress. When η0 / Mw 6.8 exceeds the upper limit value, the number of long-chain branches tends to be insufficient, and when it is below the lower limit value, the length of the long-chain branches tends to be insufficient.

[0171] The relationship between the zero-shear viscosity [η0(P)] and the weight-average molecular weight (Mw) is considered to depend on the content and length of long-chain branches in the ethylene-based polymer. The higher the long-chain branch content and the shorter the length of the long-chain branches, the closer the zero-shear viscosity [η0(P)] is to the lower limit of the claim range. Conversely, the lower the long-chain branch content and the longer the length of the long-chain branches, the closer the zero-shear viscosity [η0(P)] is to the upper limit of the claim range.

[0172] Here, the long-chain branch is defined as a branched structure with a length equal to or greater than the molecular weight between entanglement points (Me) contained in the ethylene-based polymer. It is known that the melt physical properties and molding processability of the ethylene-based polymer change significantly due to the introduction of long-chain branches (for example, Ichio Matsuura et al., "Polyethylene Technology Reader", Industrial Research Society, 2001, p. 32, 36).

[0173] In the mechanism by which the ethylene-based polymer is formed, the inventors estimate that a "macromonomer", which is a polymer having a number-average molecular weight of 4000 or more and 20000 or less, preferably 4000 or more and 15000 or less, with terminal vinyl groups, is formed by copolymerizing ethylene and an α-olefin having 4 to 10 carbon atoms in the presence of a catalyst component for olefin polymerization containing component (A), component (C), and the solid carrier (S). Subsequently, the macromonomer is copolymerized competitively with the polymerization of ethylene and an α-olefin having 4 to 10 carbon atoms by a catalyst component for olefin polymerization containing component (B), component (C), and the solid carrier (S), thereby generating long-chain branches in the ethylene-based polymer.

[0174] The higher the composition ratio of the macromonomer to ethylene ([macromonomer] / [ethylene]) in the polymerization system, the higher the long-chain branching content. Since [macromonomer] / [ethylene] can be increased by increasing the ratio of component (A) in the olefin polymerization catalyst, that is, the molar ratio of component (A) to the total of component (A) and component (B) ([A] / [A + B]), increasing ([A] / [A + B]) increases the long-chain branching content. Also, increasing the composition ratio of hydrogen to ethylene (hydrogen / ethylene) in the polymerization system decreases the molecular weight of the macromonomer, so the length of the long-chain branches introduced into the ethylene-based polymer becomes shorter.

[0175] Therefore, by increasing or decreasing [A] / [A + B] and hydrogen / ethylene, η0 / Mw within the above range 6.8 an ethylene-based polymer can be produced. For example, based on 100% of the total of component (A) and component (B) contained in the olefin polymerization catalyst, the molar ratio of component (A) is usually 1 to 99%, preferably 30 to 99%, more preferably 60 to 99%. In addition to these, polymerization conditions for controlling the amount of long-chain branches are disclosed, for example, in WO 2007 / 034920 pamphlet.

[0176] (4) The ratio of the intrinsic viscosity [η] (dl / g) measured in decalin at 135°C to the 0.776th power of the weight-average molecular weight (Mw 0.776 ) measured by the GPC-viscosity detector method (GPC-VISCO), [η] / Mw 0.776 is 0.90×10 -4 or more and 1.65×10 -4 or less. That is, in the ethylene-based polymer used in the present invention, [η] and Mw satisfy the following formula (Eq-2) 0.90×10 -4 ≦[η] / Mw 0.776 ≦1.65×10 -4 ---(Eq-2) Here, the lower limit is preferably 0.95×10 -4 , more preferably 1.00×10 -4 , and the upper limit is preferably 1.55×10 -4, more preferably 1.45×10 -4 .

[0177] [η] / Mw 0.776 is 0.90×10 -4 or more and 1.65×10 -4 or less, which is synonymous with the fact that when [η] and Mw are plotted on a double logarithmic scale, log([η])) and log(Mw) exist in the region defined by the following formula (Eq-2´). 0.776Log(Mw)-4.046≦Log([η]))≦0.776Log(Mw)-3.783 --- (Eq-2´)

[0178] When long-chain branches are introduced into the ethylene-based polymer, it is known that the intrinsic viscosity [η] (dl / g) is smaller for the same molecular weight compared to a linear ethylene-based polymer without long-chain branches (for example, Walther Burchard, ADVANCES IN POLYMER SCIENCE, 143, Branched PolymerII, p.137 (1999)). Therefore, when [η] / Mw 0.776 of the present ethylene-based polymer is below the above upper limit value, particularly 1.65×10 -4 or less, it has a large number of long-chain branches and the moldability and fluidity of the ethylene-based polymer are excellent.

[0179] As described above, by increasing the ratio ([A] / [A+B]) of component (A) in the olefin polymerization catalyst, the long-chain branch content increases. Therefore, by increasing or decreasing [A] / [A+B], an ethylene-based polymer (α) having the intrinsic viscosity [η] of the claim can be produced. For the purpose of suppressing variations in physical property values, the ethylene-based polymer particles obtained by the polymerization reaction and other components added as desired can also be melted, kneaded, and pelletized by any method.

[0180] The ethylene-based polymer obtained in the present invention may be pelletized by the following method. (i) A method of mechanically blending the ethylene-based polymer and other components added as desired using an extruder, kneader, etc. and cutting them into a predetermined size. (ii) A method in which an ethylene-based polymer and other components added as desired are dissolved in a suitable good solvent (for example, hydrocarbon solvents such as hexane, heptane, decane, cyclohexane, benzene, toluene, and xylene), then the solvent is removed, and then mechanically blended using an extruder, kneader, etc. and cut into a predetermined size.

[0181] The ethylene-based polymer obtained in the present invention may, within a range not impairing the object of the present invention, be blended with additives such as a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a pigment, a dye, a nucleating agent, a plasticizer, an anti-aging agent, a hydrochloric acid absorbent, and an antioxidant as required.

[0182] The ethylene-based polymer obtained in the present invention, and a resin composition containing a thermoplastic resin and additives as required are processed by general film forming, blow molding, injection molding, and extrusion molding. In film forming, it can be obtained by extrusion lamination molding, T-die film molding, inflation molding (air cooling, water cooling, multi-stage cooling, high-speed processing), etc. The film obtained using the ethylene-based polymer can be used as a single layer, but various functions can be imparted by making it multilayer. In that case, the coextrusion method in each of the above molding methods can be mentioned. On the other hand, lamination with paper or a barrier film (aluminum foil, vapor-deposited film, coated film, etc.) that is difficult to coextrude can be achieved by a bonding lamination molding method such as extrusion lamination molding or dry lamination method. The production of high-functional products by multilayer formation by the coextrusion method in blow molding, injection molding, and extrusion molding is possible in the same manner as in film forming.

[0183] Examples of the molded article obtained by processing the ethylene-based polymer obtained in the present invention, and a resin composition containing a thermoplastic resin and additives as required include films, blow infusion bags, blow bottles, gasoline tanks, tubes and pipes by extrusion molding, injection molded articles such as tear-off caps and daily sundries, fibers, and large molded articles by rotational molding.

[0184] Furthermore, the film obtained by processing the ethylene-based polymer obtained in the present invention and, if necessary, a resin composition containing a thermoplastic resin and an additive is suitable for various packaging films such as water product packaging bags, liquid soup packaging bags, liquid paper containers, raw laminates, special-shaped liquid packaging bags (standing pouches, etc.), standard bags, heavy bags, wrap films, sugar bags, oil product packaging bags, food packaging, protective films, infusion bags, agricultural materials, etc. It can also be used as a multilayer film by laminating it with a base material such as nylon or polyester.

Examples

[0185] Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples in any way. In the following examples and comparative examples, the physical properties of the obtained ethylene-based polymer were measured as follows.

[0186] <Melt Flow Rate (MFR)> It was measured under the conditions of 190 °C and a load of 2.16 kg (kgf).

[0187] <Density (D)> The strand obtained during the MFR measurement was heat-treated at 100 °C for 30 minutes, and then left at room temperature for 1 hour, and then measured by the density gradient tube method.

[0188] <Melt Tension (MT)> The melt tension (MT) (unit: g) at 190 °C was determined by measuring the stress when stretched at a constant speed. For the measurement, a capillary rheometer manufactured by Toyo Seiki Seisakusho: Capilograph 1D was used. The conditions were resin temperature 190 °C, melting time 6 minutes, barrel diameter 9.55 mm φ, extrusion speed 15 mm / min, winding speed 24 m / min (if the molten filament breaks, the winding speed is decreased by 5 m / min), nozzle diameter 2.095 mm φ, and nozzle length 8 mm.

[0189] <Shear Viscosity (η * )> The shear viscosity [η * (1.0)] (P) at 200 °C and an angular velocity of 1.0 rad / s was measured by the following method. The shear viscosity (η * ) is measured for the angular velocity [ω (rad / s)] dispersion of the shear viscosity (η * ) at a measurement temperature of 200 °C in the range of 0.01 ≤ ω ≤ 100. For the measurement, a viscoelasticity measuring device Physica MCR301 manufactured by Anton Paar was used. A 25 mmφ parallel plate was used as the sample holder, and the sample thickness was set to approximately 2.0 mm. The measurement points were set to 5 points per digit of ω. The strain amount was appropriately selected in the range of 3 - 10% so that the torque in the measurement range was detectable and torque overshoot did not occur.

[0190] The sample used for the shear viscosity measurement was produced by press molding to a thickness of 2 mm under the conditions of a preheating temperature of 190 °C, a preheating time of 5 minutes, a heating temperature of 190 °C, a heating time of 2 minutes, a heating pressure of 100 kgf / cm 2 , a cooling temperature of 20 °C, a cooling time of 5 minutes, and a cooling pressure of 100 kgf / cm 2 using a press molding machine manufactured by Shindo Metal Works.

[0191] <Zero shear viscosity (η0)> The zero shear viscosity (η0) (P) at 200 °C was determined by the following method. At a measurement temperature of 200 °C, the angular velocity ω (rad / s) dispersion of the shear viscosity (η * ) is measured in the range of 0.01 ≤ ω ≤ 100. For the measurement, a viscoelasticity measuring device Physica MCR301 manufactured by Anton Paar was used. A 25 mmφ parallel plate was used as the sample holder, and the sample thickness was set to approximately 2.0 mm. The measurement points were set to 5 points per digit of ω. The strain amount was appropriately selected in the range of 3 - 10% so that the torque in the measurement range was detectable and torque overshoot did not occur.

[0192] The sample used for the shear viscosity measurement was produced by press molding to a thickness of 2 mm under the conditions of a preheating temperature of 190 °C, a preheating time of 5 minutes, a heating temperature of 190 °C, a heating time of 2 minutes, a heating pressure of 100 kgf / cm 2, Cooling temperature 20°C, cooling time 5 minutes, cooling pressure 100 kgf / cm 2 The measurement sample was prepared by press-molding it to a thickness of 2 mm under the conditions of

[0193] The zero-shear viscosity (η0) was calculated by fitting the Carreau model of the following formula (Eq-3) to the measured rheology curve [angular velocity (ω) dispersion of shear viscosity (η * )] by the non-linear least squares method. Η * = η0〔1 + (λω) a 〕 (n-1) / a ---(Eq-3)

[0194] Here, λ is a parameter with the dimension of time, and n represents the power law index of the material. The fitting by the non-linear least squares method was performed so that d in the following formula (Eq-4) was minimized.

[0195]

Equation

[0196] <Number-average molecular weight (Mn), weight-average molecular weight (Mw), Z-average molecular weight (Mz), molecular weight distribution (Mw / Mn, Mz / Mw)> Using a Waters GPC-viscosity detector (GPC-VISCO) GPC / V2000, the measurement was performed as follows.

[0197] Shodex AT-G was used for the guard column, two AT-806 columns were used for the analytical column, a differential refractometer and a 3-capillary viscometer were used for the detector, the column temperature was set at 145 °C, o-dichlorobenzene containing 0.3 wt% of BHT as an antioxidant was used as the mobile phase, the flow rate was 1.0 ml / min, and the sample concentration was 0.1 wt%. Standard polystyrene manufactured by Tosoh Corporation was used. For molecular weight calculation, the measured viscosity was calculated from the viscometer and refractometer, and the number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), and molecular weight distribution (Mw / Mn, Mz / Mw) were determined from the measured universal calibration.

[0198] <Intrinsic viscosity [η]> Approximately 20 mg of the measurement sample was dissolved in 15 ml of decalin, and the specific viscosity η was measured in an oil bath at 135 °C. sp After adding 5 ml of decalin solvent to this decalin solution for dilution, the specific viscosity η was measured in the same manner. sp This dilution operation was repeated two more times, and the value of η / C when extrapolating the concentration (C) to 0 as shown in the following formula (Eq-5) was determined as the intrinsic viscosity [η] (unit: dl / g). sp [η]=lim(η / C) (C→0) --- (Eq-5) [η]=lim(η sp / C) (C→0) --- (Eq-5)

[0199] [Synthesis of Component (A) and Component (B)] [Synthesis Example 1] Dimethylsilylene(2-indenyl)(4-(3,5-di-tert-butyl-4-methoxyphenyl)-1,5,6,7-tetrahydro-s-1-indacenyl)zirconium dichloride represented by the following formula (A-1) (hereinafter also referred to as "Component (A-1)") was synthesized by the method described in JP-A-2019-059933.

[0200] [Chemical Formula]

[0201] [Synthesis Example 2] Dimethylsilylene(2 - indenyl)(4-(3,5 - di - tert - butyl - 4 - methoxyphenyl)-7 - methoxy - 1 - indenyl)zirconium dichloride represented by the following formula (A - 2) (hereinafter also referred to as "component (A - 2)") was synthesized by the method described in JP - A - 2019 - 059933.

[0202]

Chemical formula

[0203] <Synthesis Example 3> Dimethylsilylene(2 - indenyl)(1 - indenyl)zirconium dichloride represented by the following formula (A - 3) (hereinafter also referred to as "component (A - 3)") was synthesized by the method described in JP - A - 11 - 292934.

[0204]

Chemical formula

[0205] <Synthesis Example 4> Dimethylsilylene(2 - indenyl)(2 - methyl - 1 - indenyl)zirconium dichloride represented by the following formula (A - 4) (hereinafter also referred to as "component (A - 4)") was synthesized by the method described in JP - A - 2019 - 059933.

[0206]

Chemical formula

[0207] <Synthesis Example 5> Dimethylsilylene(2 - indenyl)(4,7 - dimethyl - 1 - indenyl)zirconium dichloride represented by the following formula (A - 5) (hereinafter also referred to as "component (A - 5)") was synthesized by the method described in JP - A - 2019 - 059933.

[0208]

Chemical formula

[0209] <Synthesis Example 6> Dimethylsilylene(3-n-propylcyclopentadienyl)(cyclopentadienyl)zirconium dichloride represented by the following formula (A-6) (hereinafter also referred to as "Component (A-6)") was synthesized by the method described in Japanese Patent No. 5455354.

[0210] [Chemical Formula]

[0211] <Synthesis Example 7> Dimethylsilylene(3-n-butyl-2-methyl-1-indenyl)(cyclopentadienyl)zirconium dichloride represented by the following formula (A-7) (hereinafter also referred to as "Component (A-7)") was synthesized by the method described in JP-A-2019-059934.

[0212] [Chemical Formula]

[0213] <Synthesis Example 8> Isopropylidene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium dichloride represented by the following formula (B-1) (hereinafter also referred to as "Component (B-1)") was synthesized based on the method described in JP-A-4-69394. [Chemical Formula]

[0214] [Example 1] [Preparation of Solid Catalyst Component (X)] In a reactor with a stirrer having an internal volume of 270 liters, under a nitrogen atmosphere, as the solid support (S), silica 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 of (fired at 250 °C) was suspended in 77 liters of toluene and then cooled to 0 - 5 °C. To this suspension, 20.4 liters of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atoms) as component (C) was added dropwise over 30 minutes. At this time, the temperature inside the system was maintained at 0 - 5 °C. Subsequently, after reacting at 0 - 5 °C for 30 minutes, the temperature was raised to 95 - 100 °C over about 1.5 hours, and then the reaction was continued at 95 - 100 °C for 4 hours. Thereafter, 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 58.0 liters was prepared. When a part of the obtained slurry component was sampled and its concentration was examined, the slurry concentration was 248.0 g / L and the Al concentration was 1.21 mol / L.

[0215] Among these, 0.6 milliliters (solid content mass 0.15 g) was charged into a Schlenk reactor with a stir bar and an internal volume of 30 milliliters under a nitrogen atmosphere, and 12.6 milliliters of toluene was added. Next, 2.4 μmol of the toluene solution of component (A - 1) obtained in Synthesis Example 1 and 1.3 μmol of the toluene solution of component (B - 1) obtained in Synthesis Example 4 were added in terms of Zr (molar ratio of component (A) / component (B) = 65 / 35). After contacting these at a system temperature of 20 - 25 °C for 1 hour, the supernatant was removed by decantation, and after further washing twice with 20 milliliters of hexane, a hexane slurry of a solid catalyst component (X - 1) with a total volume of 15.24 milliliters was prepared.

[0216] <Production of Ethylene - based Polymer> Into a 1-liter SUS autoclave with a stirrer blade that had been sufficiently purged with nitrogen, 500 milliliters of heptane was added under a nitrogen atmosphere. Then, ethylene was passed through to saturate the liquid and gas phases with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30 mg of the solid catalyst component (X-1) as a solid content were charged. After that, the temperature was raised to 80 °C and the pressure was raised to 0.8 MPaG using an ethylene-hydrogen mixed gas with a hydrogen concentration of 0.1 vol%, and a polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum dried at 80 °C for 10 hours to obtain 72.6 g of an ethylene-based polymer. The polymerization activity per solid catalyst was 2,420 g / g-cat.

[0217] To the obtained ethylene-based polymer, 0.1 mass% of IrganoX1076 (trade name, manufactured by Ciba Specialty Chemicals Inc.) and 0.1 mass% of Irgafos168 (trade name, manufactured by Ciba Specialty Chemicals Inc.) were added as heat stabilizers, and using a Laboplast Mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), melt kneading was carried out at a resin temperature of 180 °C and a rotation speed of 50 rpm for 5 minutes. Further, this molten polymer was cooled using a press molding machine (manufactured by Kando Metal Industry Co., Ltd.) under the conditions of a cooling temperature of 20 °C, a cooling time of 5 minutes, and a cooling pressure of 100 kg / cm 2 The obtained sample was used as a measurement sample, and physical property measurements were carried out. The results are shown in Table 8.

[0218] [Example 2] [Preparation of Solid Catalyst Component (X)] In Example 1, a slurry of the solid catalyst component (X-2) was prepared in the same manner as in Example 1, except that 2.8 μmol of component (A-2) was used instead of 2.4 μmol of component (A-1), 1.3 μmol of component (B-1) was changed to 0.4 μmol, and the molar ratio of component (A) / component (B) was set to 80 / 20.

[0219] [Production of Ethylene-Based Polymer] After adding 500 milliliters of heptane to a 1-liter SUS autoclave with a stirrer blade that had been sufficiently purged with nitrogen under a nitrogen atmosphere, ethylene was passed through to saturate the liquid and gas phases with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30 mg of the solid catalyst component (X-2) as a solid content were charged. Then, the temperature was raised to 80 °C and the pressure was raised to 0.8 MPaG using an ethylene-hydrogen mixed gas with a hydrogen concentration of 0.1 vol%, and a polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum dried at 80 °C for 10 hours to obtain 78.9 g of an ethylene-based polymer. The polymerization activity per gram of solid catalyst was 2,630 g / g-cat. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the obtained sample was used as a measurement sample for physical property measurement. The results are shown in Table 8.

[0220] [Example 3] <Preparation of Solid Catalyst Component (X)> In Example 1, a slurry of the solid catalyst component (X-3) was prepared in the same manner as in Example 1, except that 2.6 μmol of component (A-3) was used instead of 2.4 μmol of component (A-1), 1.3 μmol of component (B-1) was changed to 1.0 μmol, and the molar ratio of component (A) / component (B) was set to 72 / 28.

[0221] <Production of Ethylene-Based Polymer> Into a 1-liter SUS autoclave with a stirrer blade that had been sufficiently purged with nitrogen, 500 milliliters of heptane was added under a nitrogen atmosphere. Then, ethylene was passed through to saturate the liquid and gas phases with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30 mg of the solid catalyst component (X-3) as a solid content were charged. After that, the temperature and pressure were raised to 80 °C and 0.8 MPaG using an ethylene-hydrogen mixed gas with a hydrogen concentration of 0.1 vol%, and a polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum dried at 80 °C for 10 hours to obtain 149.3 g of an ethylene-based polymer. The polymerization activity per gram of the solid catalyst was 4,980 g / g-cat. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the obtained sample was used as a measurement sample for physical property measurement. The results are shown in Table 8.

[0222] [Example 4] <Preparation of Solid Catalyst Component (X)> In Example 1, a slurry of the solid catalyst component (X-4) was prepared in the same manner as in Example 1, except that 3.3 μmol of component (A-4) was used instead of 2.4 μmol of component (A-1), 0.4 μmol of component (B-1) was changed to 1.3 μmol, and the molar ratio of component (A) / component (B) was set to 90 / 10.

[0223] <Production of Ethylene-Based Polymer> Into a 1-liter SUS autoclave with a stirrer blade that had been fully purged with nitrogen, 500 milliliters of heptane was added under a nitrogen atmosphere. Then, ethylene was passed through to saturate the liquid and gas phases with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30 mg of the solid catalyst component (X-4) as a solid content were charged. After that, the temperature was raised to 80 °C and the pressure was raised to 0.8 MPaG using an ethylene-hydrogen mixed gas with a hydrogen concentration of 0.1 vol%, and a polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum dried at 80 °C for 10 hours to obtain 81.6 g of an ethylene-based polymer. The polymerization activity per gram of the solid catalyst was 2,720 g / g-cat. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the obtained sample was used as a measurement sample for physical property measurement. The results are shown in Table 8.

[0224] [Example 5] <Preparation of Solid Catalyst Component (X)> In Example 1, a slurry of the solid catalyst component (X-5) was prepared in the same manner as in Example 1, except that 2.9 μmol of component (A-5) was used instead of 2.4 μmol of component (A-1), 1.3 μmol of component (B-1) was changed to 0.7 μmol, and the molar ratio of component (A) / component (B) was set to 80 / 20.

[0225] <Production of Ethylene-Based Polymer> Into a 1-liter SUS autoclave with a stirrer blade that had been fully purged with nitrogen, 500 milliliters of heptane was added under a nitrogen atmosphere. Then, ethylene was passed through to saturate the liquid and gas phases with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30 mg of the solid catalyst component (X-5) as a solid content were charged. After that, the temperature was raised to 80 °C and the pressure was raised to 0.8 MPaG using an ethylene-hydrogen mixed gas with a hydrogen concentration of 0.1 vol%, and a polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum dried at 80 °C for 10 hours to obtain 66.2 g of an ethylene-based polymer. The polymerization activity per gram of the solid catalyst was 2,210 g / g-cat. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the obtained sample was used as a measurement sample for physical property measurement. The results are shown in Table 8.

[0226] [Production Example 1] [Preparation of Solid Catalyst Component (X)] In Example 1, a slurry of the solid catalyst component (X-6) was prepared in the same manner as in Example 1, except that 2.0 μmol of component (A-6) was used instead of 2.4 μmol of component (A-1), 1.3 μmol of component (B-1) was changed to 1.6 μmol, and the molar ratio of component (A) / component (B) was set to 55 / 45.

[0227] [Production of Ethylene-Based Polymer] A 1-liter SUS autoclave with a stirrer blade, which was fully purged with nitrogen, was charged with 500 milliliters of heptane under a nitrogen atmosphere. Then, ethylene was passed through to saturate the liquid and gas phases with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 20 mg of the solid catalyst component (X-6) as a solid content were charged. After that, the temperature and pressure were raised to 80 °C and 0.8 MPaG using an ethylene-hydrogen mixed gas with a hydrogen concentration of 0.1 vol%, and a polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum dried at 80 °C for 10 hours to obtain 67.6 g of an ethylene-based polymer. The polymerization activity per gram of the solid catalyst was 3,380 g / g-cat. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the obtained sample was used as a measurement sample for physical property measurement. The results are shown in Table 8.

[0228] [Production Example 2] [Preparation of Solid Catalyst Component (X)] In Example 1, a slurry of the solid catalyst component (X-7) was prepared in the same manner as in Example 1, except that 2.8 μmol of component (A-7) was used instead of 2.4 μmol of component (A-1), 1.3 μmol of component (B-1) was changed to 0.7 μmol, and the molar ratio of component (A) / component (B) was set to 80 / 20.

[0229] [Production of Ethylene-Based Polymer] Into a 1-liter SUS autoclave with a stirrer blade that had been sufficiently purged with nitrogen, 500 milliliters of heptane was added under a nitrogen atmosphere. Then, ethylene was passed through to saturate the liquid and gas phases with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 60 mg of the solid catalyst component (X-7) as a solid content were charged. After that, the temperature and pressure were raised to 80 °C and 0.8 MPaG using an ethylene-hydrogen mixed gas with a hydrogen concentration of 0.1 vol%, and a polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was vacuum dried at 80 °C for 10 hours to obtain 143.2 g of an ethylene-based polymer. The polymerization activity per gram of the solid catalyst was 2,387 g / g-cat. The obtained ethylene-based polymer was melt-kneaded and cooled in the same manner as in Example 1, and the obtained sample was used as a measurement sample for physical property measurement. The results are shown in Table 8.

[0230]

Table 8

[0231] Comparing Examples 1 to 5 with Production Examples 1 and 2, although the addition amount of 1-hexene is the same, the density of the ethylene-based polymer is low, indicating that the 1-hexene response of density is excellent. That is, in the examples of the present invention, it is clear that an ethylene-based polymer with a large amount of long-chain branches and excellent moldability can be produced with high production efficiency in terms of reducing the amount of 1-hexene used.

Claims

1. A catalyst for olefin polymerization comprising the following component (A), the following component (B), the following component (C) and a solid carrier (S). Component (A): A transition metal compound represented by the following general formula (1); 【Chemical 1】 [In 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 compound [A] is electrically neutral, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating 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 derivative group. When n is 2 or more, the groups represented by 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, Q １ is a Group 14 atom of the periodic table, R １ 、 R ２ 、 R ３ 、 R ４ 、 R ５ 、 R ６ 、 R ７ 、 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 ８ is a hydrogen atom, R １ ~R ６ Among adjacent substituents of R １ ~R ６ , they may combine with each other to form a ring which may have a substituent. R ７ to R １２ Among the adjacent substituents, they may combine with each other to form a ring which may have a substituent. R １３ and R １４ may be joined together to form a ring containing Q １ which may have substituents.] Component (B): A transition metal compound represented by the following general formula (2); [Chemical 2] [In formula (2), M is a Group 4 transition metal atom of the periodic table, Xs are each independently an atom or a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a phosphorus-containing group, Q ２ is a group selected from hydrocarbon groups having 1 to 20 carbon atoms, halogen-containing groups, silicon-containing groups, germanium-containing groups, and tin-containing groups, R １５ to R ２６ are each independently selected from a hydrogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group, and two adjacent groups may be linked to form a ring.] Component (C): At least one compound selected from the group consisting of an organometallic compound (c-1) represented by the following general formulas (3) to (5), an organoaluminum oxy compound (c-2), and a compound (c-3) that reacts with component (A) and component (B) to form an ion pair; R ａ ｍ Al(OR ｂ ) ｎ H ｐ X ｑ ・・・(3) [In formula (3), R ａ and R ｂ each independently represents a hydrocarbon group having 1 to 15 carbon atoms, X represents a halogen atom, m is a number where 0 < m ≤ 3, n is a number where 0 ≤ n < 3, p is a number where 0 ≤ p < 3, q is a number where 0 ≤ q < 3, and m + n + p + q = 3.] M ａ AlR ａ ４ ...(4) [In formula (4), M ａ represents Li, Na or K, and R ａ represents a hydrocarbon group having 1 to 15 carbon atoms.] R ａ ｒ M ｂ R ｂ ｓ X ｔ ...(5) [In formula (5), R ａ and R ｂ each independently represent a hydrocarbon group having 1 to 15 carbon atoms, M ｂ is selected from Mg, Zn, and Cd, X represents a halogen atom, r satisfies 0 < r ≤ 2, s satisfies 0 ≤ s ≤ 1, t satisfies 0 ≤ t ≤ 1, and r + s + t = 2.]

2. In the above general formula (1), M is a zirconium atom or a hafnium atom, Xs are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or an oxygen-containing group, Q １ is a carbon atom or a silicon atom, R １ to R ６ and R ９ to R １４ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, R ７ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an aromatic heterocyclic five-membered ring group containing at least one atom selected from the group consisting of nitrogen, oxygen and sulfur, The olefin polymerization catalyst according to claim 1.

3. In the above general formula (1), Q １ is a silicon atom, R １ and R ６ are hydrogen atoms, R ２ to R ５ and R ９ to R １４ is each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group or a nitrogen-containing group, the olefin polymerization catalyst according to claim 2.

4. In the above general formula (1), R ９ The olefin polymerization catalyst according to claim 3, wherein R is an aromatic hydrocarbon group having 6 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, or a nitrogen-containing group.

5. The catalyst for olefin polymerization according to any one of Claims 1 to 4, comprising a solid catalyst component formed from a solid carrier (S), component (C) and component (A), and a solid catalyst component formed from a solid carrier (S), component (C) and component (B).

6. The catalyst for olefin polymerization according to any one of Claims 1 to 4, comprising a solid catalyst component formed from a solid carrier (S), component (A), component (B) and component (C).

7. The catalyst for olefin polymerization according to any one of claims 1 to 6, wherein the component (C) is an organoaluminum oxy compound and the solid carrier (S) is a porous oxide.

8. A process for producing an ethylene-based polymer, which comprises polymerizing ethylene alone or copolymerizing ethylene with an olefin having 3 to 20 carbon atoms in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 7.

9. The process for producing an ethylene-based polymer according to claim 8, wherein the ethylene-based polymer is a copolymer of ethylene and an α-olefin having 4 to 20 carbon atoms and satisfies the following requirements (1) to (4): (1) The melt flow rate (MFR) at 2.16 kg load at 190 °C is 0.1 g / 10 min or more and 30 g / 10 min or less; (2) having a density of 875 kg / m ３ or more and 945 kg / m ３ or less; (3) Zero-shear viscosity [η ０ (P)] at 200 °C and the ratio (η ６．８ / Mw ０ ) of the sixth power of the weight-average molecular weight (Mw ６．８ ) measured by the GPC-viscosity detector method (GPC-VISCO) is 0.03 × 10 -３０ or more and 7.5 × 10 -３０ or less; (4) The ratio of the intrinsic viscosity [[η]] (dl / g) measured in decalin at 135°C to the 0.776th power of the weight average molecular weight (Mw ０．７７６ ) measured by the GPC-viscosity detector method (GPC-VISCO) ([η] / Mw ０．７７６ ) is 0.90 × 10 -４ or more and 1.65 × 10 -４ or less.

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