Transition metal compound, catalyst for olefin polymerization, and method for producing olefin polymer

Abstract

To provide a transition metal compound that can produce an olefin polymer containing a large number of molecular chains having vinyl group at the terminal and having a small molecular weight with high catalytic activity.SOLUTION: Provided is a transition metal compound [A] represented by formula [1]. (M is a Group 4 transition metal atom of the periodic table; n is an integer from 1 to 4; X is H, halogen atom, etc.; Q is the Group 14 atom of the periodic table; R1 to R14 each independently is H, hydrocarbon group or the like having 1 to 40 carbon atoms.).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a transition metal compound, a catalyst for olefin polymerization, and a method for producing an olefin polymer using the same.

Background Art

[0002] Polymers having a polymerizable functional group at one end are expected to be used in a wide range of fields by taking advantage of the characteristics of their structures. For example, a polymer having a vinyl group at the end and a relatively low molecular weight can be used as a macromonomer in macromonomer copolymerization to enable the synthesis of polymers having many long-chain branches. In addition, such polymers can also be widely applied to polar resin composite materials and the like by functionalizing the unsaturated bond in the polymerizable functional group (see Patent Document 1, etc.).

[0003] Therefore, conventionally, techniques have been developed for efficiently producing a polymer having a vinyl group at the end and a relatively low molecular weight. For example, Patent Document 2 discloses a method for efficiently producing an olefin polymer having a vinyl group at the end and a relatively low molecular weight using a specific metallocene catalyst.

[0004] On the other hand, Patent Documents 3 to 5, etc. disclose methods for producing ethylene-based polymers using a crosslinked (2-indenyl)(1-indenyl) type transition metal compound as a catalyst.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] However, in the prior art for producing a polymer having a vinyl group at the terminal and a relatively low molecular weight, there is still room for further improvement from the viewpoint of increasing the ratio of the molecular chains having a vinyl group at the terminal.

[0007] Therefore, an object of the present invention is to provide a transition metal compound, a catalyst for olefin polymerization, and a method for producing an olefin polymer that contain many molecular chains having a vinyl group at the terminal and have a low molecular weight, and can be produced with high catalytic activity.

MEANS FOR SOLVING THE PROBLEMS

[0008] The present inventors intensively studied to solve the above problems, and found that the above problems can be solved by introducing a substituent at a specific position of the 2-indenyl ring of a crosslinked (2-indenyl)(1-indenyl) type transition metal compound, and completed the present invention.

[0009] The gist of the present invention is as follows. [1] A transition metal compound [A] represented by the following general formula [1].

[0010]

CHEMICAL FORMULA

[0011] (In the general formula [1], M is a Group 4 transition metal atom of the periodic table, n is an integer of 1 to 4 selected so that the transition metal 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 is an atom of Group 14 of the periodic table. R 1 、R 2 、R 5 、R 6 、R 7 、R 8 、R 10 、R 11 、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 3 and R 4 are each independently a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. R 9 and R 12 are 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 (however, R 9 is not a substituent represented by the following general formula [1-1].

[0012]

Chemical formula

[0013] (In the general formula [1-1], R 9a 、R 9b 、R 9c 、R 9d and R 9e are each independently a hydrogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a sulfur-containing group. * represents a bond to the indenyl ring.)) R 1 ~R 6 Among them, adjacent substituents may combine with each other to form a ring which may have substituents. R 7 ~R 12 Among them, adjacent substituents may combine with each other to form a ring which may have substituents. R 13 and R 14 may combine with each other to form a ring containing Q, and this ring may have substituents. )

[0014] [2] In the general formula [1], M is a zirconium atom or a hafnium atom, X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or an oxygen-containing group, Q is a carbon atom or a silicon atom, R 1 R 2 R 5 R 6 R 8 R 10 R 11 R 13 and R 14 are independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms or a sulfur-containing group having 1 to 20 carbon atoms, R 3 and R 4 are independently a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms or a sulfur-containing group having 1 to 20 carbon atoms, and may combine with each other to form a ring which may have substituents. R 7is an optionally substituted aromatic heterocyclic five-membered ring substituent having a substituent which is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or an atom selected from nitrogen, oxygen, and sulfur in the heterocyclic ring, R 9 and R 12 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms, or a sulfur-containing group having 1 to 20 carbon atoms, and the transition metal compound [A] of the above [1].

[0015] [3] In the general formula [1], Q is a silicon atom, R 1 , R 2 , R 5 , R 6 , R 8 , R 10 , R 11 , R 13 and R 14 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms, R 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms, and may be bonded to each other to form an optionally substituted ring, R 9 and R 12 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms, and the transition metal compound [A] of the above [2].

[0016] [4] In the general formula [1], the transition metal compound [A] of the above [3], wherein R 1 and R 6 are hydrogen atoms. [5] In the general formula [1], R 2 and R 5 are hydrogen atoms, and the transition metal compound [A] of [4].

[0017] [6] In the general formula [1], R 7 and R 8 are hydrogen atoms, and the transition metal compound [A] of [5]. [7] In the general formula [1], R 10 and R 11 are hydrogen atoms, and the transition metal compound [A] of [6].

[0018] [8] In the general formula [1], R 3 and R 4 at least one of which is a hydrocarbon group having 1 to 20 carbon atoms, and the transition metal compound [A] of [7].

[0019] [9] In the general formula [1], R 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, and may be bonded to each other to form a ring which may have a substituent, and the transition metal compound [A] of [8].

[0020]

[10] In the general formula [1], R 9 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the transition metal compound [A] of [8] or [9].

[0021]

[11] In the general formula [1], R 12 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the transition metal compound [A] of

[10] .

[0022]

[12] A catalyst for olefin polymerization containing the transition metal compound [A] according to any one of [1] to

[11] .

[0023]

[13] Further, [B][B-1] organometallic compounds, [B-2] organoaluminum oxy compounds, and at least one compound selected from the group consisting of compounds that react with [B-3] transition metal compounds [A] to form ion pairs, the olefin polymerization catalyst of

[12] above.

[0024]

[14] A method for producing an olefin polymer, comprising a step of polymerizing an olefin in the presence of the olefin polymerization catalyst of

[12] or

[13] above.

[0025]

[15] The method for producing an olefin polymer according to

[14] above, wherein the step of polymerizing the olefin is a step of homopolymerizing ethylene or a step of copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms.

Effects of the Invention

[0026] According to the transition metal compound, olefin polymerization catalyst, and method for producing an olefin polymer according to the present invention, an olefin polymer (especially an ethylene-based polymer) containing many molecular chains having a vinyl group at the terminal and having a small molecular weight can be produced with high catalytic activity.

Modes for Carrying Out the Invention

[0027] Hereinafter, the transition metal compound and the like according to the present invention will be described in more detail. [Transition metal compound [A]] The transition metal compound [A] according to the present invention (hereinafter sometimes referred to as "component (A)") is represented by the following general formula [1].

[0028]

Chemical formula

[0029] 《M, n, X》 In the general formula [1], M is a Group 4 transition metal atom of the periodic table, preferably a zirconium atom or a hafnium atom, more preferably a zirconium atom.

[0030] n is an integer of 1 to 4 selected so that the transition metal compound [A] is electrically neutral, preferably 1 or 2. X is a hydrogen atom, a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone pair of electrons. The anionic ligand is a halogen-containing group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a boron-containing group, an aluminum-containing group or a conjugated diene-based derivative group. X is preferably a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or an oxygen-containing group.

[0031] When n is 2 or more, a plurality of Xs may be the same as or different from each other, and may be bonded to each other to form a ring. Further, when a plurality of the rings exist, the rings may be the same as or different from each other.

[0032] Examples of the halogen atom include fluorine, chlorine, bromine, iodine, etc., preferably chlorine or bromine. Examples of the hydrocarbon group include, for example, linear or branched alkyl groups such as methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group (butan-2-yl group), tert-butyl group (2-methylpropan-2-yl group), iso-butyl group (2-methylpropyl group), pentan-2-yl group, 2-methylbutyl group, iso-pentyl group (3-methylbutyl group), neopentyl group (2,2-dimethylpropyl group), siamil 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), 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); 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, terphenyl group, binaphthyl group, acenaphthylenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group, etc. can be mentioned.

[0033] 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.

[0034] 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.

[0035] Among the halogen-containing groups, a pentafluorophenyl group is preferable. Examples of the silicon-containing group include trimethylsilyl group, triethylsilyl group, tri-iso-propylsilyl group, diphenylmethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiphenylsilyl group, triphenylsilyl group, tris(trimethylsilyl)silyl group, trimethylsilylmethyl group, etc.

[0036] Among the silicon-containing groups, a trimethylsilylmethyl group is preferable. Examples of the oxygen-containing group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, a benzyloxy group, a methoxymethoxy group, a phenoxy group, a 2,6-dimethylphenoxy group, a 2,6-di-iso-propylphenoxy group, a 2,6-di-tert-butylphenoxy group, a 2,4,6-trimethylphenoxy group, a 2,4,6-tri-iso-propylphenoxy group, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetoxy group, a perchlorate anion, and a periodate anion.

[0037] Among the oxygen-containing groups, a methoxy group, an ethoxy group, an iso-propoxy group, and a tert-butoxy group are preferred. 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).

[0038] Among the sulfur-containing groups, a triflate group (trifluoromethanesulfonate group) is preferred. 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.

[0039] Among the nitrogen-containing groups, a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a pyrrolyl group, and a bistriflylimide group are preferred. Examples of the phosphorus-containing group include a hexafluorophosphate anion.

[0040] 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.).

[0041] Examples of the aluminum-containing group include

[0042]

Chemical formula

[0043] (M represents M in the general formula (1).) Groups represented by AlR4 (where R represents hydrogen, an alkyl group, an aryl group which may have a substituent, or a halogen atom, etc.) that can form

[0044] 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 metallocyclopentene group, etc.

[0045] 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.

[0046] 《Q》 In the general formula [1], Q is an atom of Group 14 of the periodic table, such as a carbon atom, a silicon atom, a germanium atom or a tin atom, preferably a carbon atom or a silicon atom, more preferably a silicon atom.

[0047] 《R 1 ~R 14 》 In the general formula [1], R 1 、R 2 、R 5 、R 6 、R 7 、R 8 、R 10 、R 11 、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 3 and R 4 are each independently a hydrocarbon group having 1 to 40 carbon atoms, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, R 9 and R 12 are 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 (provided that R 9 is not a substituent represented by the following general formula [1-1].

[0048]

Chemical formula

[0049] (In the general formula [1-1], R 9a 、R 9b 、R 9c 、R 9d and R 9eis, independently, a hydrogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, * represents a bond to the indenyl ring. )).

[0050] R 1 ~R 14 Examples of the hydrocarbon group having 1 to 40 carbon atoms as said R

[0051] include hydrocarbon groups having 1 to 20 carbon atoms. More specific examples include the specific examples of the hydrocarbon groups listed as examples of X above. The hydrocarbon group having 1 to 40 carbon atoms is preferably a hydrocarbon group having 1 to 20 carbon atoms (excluding aromatic hydrocarbon groups) or an aromatic hydrocarbon group having 6 to 40 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms is preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms also includes substituents having an aromatic structure such as an arylalkyl group.

[0052] Examples of the hydrocarbon group having 1 to 40 carbon atoms include, 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; A linear or branched alkenyl group or an unsaturated double bond-containing group having 2 to 40 carbon atoms, 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, buta-1,3-dienyl group, penta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group, 2-methylbut-3-en-1-yl group, penta-4-en-2-yl group, prenyl group, 2-methyl-but-2-en-1-yl group, penta-3-en-2-yl group, 2-methyl-but-3-en-2-yl group, penta-1-en-3-yl group, penta-2,4-dien-1-yl group, penta-1,3-dien-1-yl group, penta-1,4-dien-3-yl group, iso-prenyl group (2-methyl-but-1,3-dien-1-yl group), penta-2,4-dien-2-yl group, hexa-5-en-1-yl group, hexa-4-en-1-yl group, hexa-3-en-1-yl group, hexa-2-en-1-yl group, 4-methyl-penta-4-en-1-yl group, 3-methyl-penta-4-en-1-yl group, 2-methyl-penta-4-en-1-yl group, hexa-5-en-2-yl group, 4-methyl-penta-3-en-1-yl group, 3-methyl-penta-3-en-1-yl group, 2,3-dimethyl-but-2-en-1-yl group, 2-methylpenta-4-en-2-yl group, 3-ethylpenta-1-en-3-yl group, hexa-3,5-dien-1-yl group, hexa-2,4-dien-1-yl group, 4-methylpenta-1,3-dien-1-yl group, 2,3-dimethyl-but-1,3-dien-1-yl group, hexa-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 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,Aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, such as 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; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, dimethylcyclopentadienyl group, n-butylcyclopentadienyl group, n-butyl-methylcyclopentadienyl group, tetramethylcyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, cyclohexadienyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, cyclooctatrienenyl group, 1-methylcyclooctyl group, 1-allylcyclooctyl group, 1-benzylcyclooctyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, norbornenyl group, norbornadienyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, 7-methylbicyclo[2.2.1]heptan-7-yl group, bicyclo[2.2.2]octan-1-yl group, bicyclo[2.2.2]octan-2-yl group, 1-adamantyl group, 2-adamantyl group, 1-(2-methyladamantyl), 1-(3-methyladamantyl), 1-(4-methyladamantyl), 1-(2-phenyladamantyl), 1-(3-phenyladamantyl), 1-(4-phenyladamantyl), 1-(3,5-dimethyladamantyl), 1-(3,5,7-trimethyladamantyl), 1-(3,5,7-triphenyladamantyl), pentalenyl group, indenyl group, fluorenyl group, indacenyl group, tetrahydroindacenyl group, benzoindenyl group, azulenyl group and other cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms; Aromatic substituents having 6 to 40 carbon atoms such as phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, duryl group, 2,6 - di - iso - propylphenyl group, 2,4,6 - tri - iso - propylphenyl group, 4 - tert - butylphenyl group, 3,5 - di - tert - butylphenyl group, allylphenyl group, (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, terphenyl group, binaphthyl group, acenaphthylenyl group, phenanthryl group, anthracenyl group, pyrenyl group, ferrocenyl group, etc. are exemplified.

[0053] Among the linear or branched alkyl groups having 1 to 40 carbon atoms, methyl group, ethyl group, 1 - propyl group, 1 - butyl group, 1 - pentyl group, 1 - hexyl group, 1 - heptyl group, 1 - octyl group, iso - propyl group, sec - butyl group, tert - butyl group, iso - butyl group, iso - pentyl group, neopentyl group, tert - pentyl group, pentan - 3 - yl group, iso - hexyl group, 1,1 - dimethylbutyl group, 3,3 - dimethylbutyl group, texyl group, 3 - methylpentan - 3 - yl group, heptan - 4 - yl group, 2,4 - dimethylpentan - 2 - yl group, 3 - ethylpentan - 3 - yl group, 4,4 - dimethylpentyl group, 4 - methylheptan - 4 - yl group, 4 - propylheptan - 4 - yl group, 2,4,4 - trimethylpentan - 2 - yl group, etc. are preferable, and methyl group, ethyl group, 1 - propyl group, 1 - butyl group, 1 - pentyl group, 1 - hexyl group, iso - propyl group, tert - butyl group, neopentyl group, 2,4 - dimethylpentan - 2 - yl group, 2,4,4 - trimethylpentan - 2 - yl group are more preferable.

[0054] Among the linear or branched alkenyl groups or unsaturated double bond-containing groups having 2 to 40 carbon atoms, vinyl group, allyl group, but-3-en-1-yl group, crotyl group, methallyl group, pent-4-en-1-yl group, prenyl group, penta-1,4-dien-3-yl group, hexa-5-en-1-yl group, 2-methylpent-4-en-2-yl group, 2-(cyclopentadienyl)propan-2-yl group, 2-(cyclopentadienyl)ethyl group, etc. are preferable, and vinyl group, allyl group, but-3-en-1-yl group, pent-4-en-1-yl group, prenyl group, hexa-5-en-1-yl group are more preferable.

[0055] Among the linear or branched alkynyl groups or unsaturated triple bond-containing groups having 2 to 40 carbon atoms, ethynyl group, prop-2-yn-1-yl group, propargyl group, but-2-yn-1-yl group, but-3-yn-1-yl group, pent-3-yn-1-yl group, pent-4-yn-1-yl group, 3-methyl-but-1-yn-1-yl group, 3,3-dimethyl-but-1-yn-1-yl group, hexa-4-yn-1-yl group, hexa-5-yn-1-yl group, etc. are preferable, and prop-2-yn-1-yl group, propargyl group, but-2-yn-1-yl group, but-3-yn-1-yl group are more preferable.

[0056] Among the aromatic-containing linear or branched alkyl groups and unsaturated double bond-containing groups having 7 to 40 carbon atoms, benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group, 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 2-(4-methylphenyl)ethyl group, 2-(2,4,6-trimethylphenyl)ethyl group, 2-(3,5-dimethylphenyl)ethyl group, 2-(2,4,6-tri-iso-propylphenyl)ethyl group, 2-(4-tert-butylphenyl)ethyl group, 2-(3,5-di-tert-butylphenyl)ethyl group, styryl group, 2-methyl-1-phenylpropan-2-yl group, 3-phenylpropyl group, cinnamyl group, neophyl group, cyclopentadienyldiphenylmethyl group, 2-(1-indenyl)propan-2-yl group, (1-indenyl)diphenylmethyl group, 2-(1-indenyl)ethyl group, 2-(9-fluorenyl)propan-2-yl group, (9-fluorenyl)diphenylmethyl group, 2-(9-fluorenyl)ethyl group, etc. are preferable, and benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 3-phenylpropyl group, cinnamyl group are more preferable.

[0057] Among the cyclic saturated and unsaturated hydrocarbon groups having 3 to 40 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, 1-methylcyclopentyl group, 1-allylcyclopentyl group, 1-benzylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-allylcyclohexyl group, 1-benzylcyclohexyl group, cycloheptyl group, cycloheptenyl group, cycloheptatrienyl group, 1-methylcycloheptyl group, 1-allylcycloheptyl group, 1-benzylcycloheptyl group, cyclooctyl group, cyclooctenyl group, cyclooctadienyl group, 4-cyclohexyl-tert-butyl group, norbornyl group, 2-methylbicyclo[2.2.1]heptan-2-yl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, pentalenyl group, indenyl group, fluorenyl group, etc. are preferable, and cyclopentyl group, cyclopentenyl group, 1-methylcyclopentyl group, cyclohexyl group, cyclohexenyl group, 1-methylcyclohexyl group, 1-adamantyl group are more preferable.

[0058] Among the aromatic substituents having 6 to 40 carbon atoms, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, prenylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrocenyl group, etc. are preferable, and phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, allylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracenyl group are more preferable.

[0059] Examples of the halogen-containing group include fluoromethyl group, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, 3,3,3-trifluoropropyl group, nonafluorobutyl group, 4,4,4-trifluorobutyl group, dodecafluorohexyl group, 6,6,6-trifluorohexyl group, chlorophenyl group, fluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, di-tert-butyl-fluorophenyl group, trifluoromethylphenyl group, bistrifluoromethylphenyl group, trifluoromethoxyphenyl group, bistrifluoromethoxyphenyl group, trifluoromethylthiophenyl group, bistrifluoromethylthiophenyl group, fluorobiphenyl group, difluorobiphenyl group, trifluorobiphenyl group, tetrafluorobiphenyl group, pentafluorobiphenyl group, di-tert-butyl-fluorobiphenyl group, trifluoromethylbiphenyl group, bistrifluoromethylbiphenyl group, trifluoromethoxybiphenyl group, bistrifluoromethoxybiphenyl group, trifluoromethyldimethylsilyl group, trifluoromethoxy group, pentafluoroethoxy group, fluorophenoxy group, difluorophenoxy group, trifluorophenoxy group, pentafluorophenoxy group, di-tert-butyl-fluorophenoxy group, trifluoromethylphenoxy group, bistrifluoromethylphenoxy group, trifluoromethoxyphenoxy group, bistrifluoromethoxyphenoxy group, difluoromethylenedioxyphenyl group, bistrifluoromethylphenyliminomethyl group, trifluoromethylthio group, and the like.

[0060] Among the halogen-containing groups, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group, a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a trifluoromethoxyphenyl group, a pentafluorobiphenyl group, a trifluoromethylbiphenyl group, a bistrifluoromethylbiphenyl group, a trifluoromethoxy group, a pentafluorophenoxy group, a bistrifluoromethylphenoxy group, a bistrifluoromethylphenoxy group, a difluoromethylene dioxyphenyl group, a trifluoromethylthio group are preferable, and a trifluoromethyl group, a fluorophenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a pentafluorobiphenyl group, a trifluoromethoxy group, a pentafluorophenoxy group are more preferable.

[0061] Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a tri-iso-propylsilyl group, a diphenylmethylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a triphenylsilyl group, a tris(trimethylsilyl)silyl group, a cyclopentadienyldimethylsilyl group, a di-n-butyl(cyclopentadienyl)silyl group, a cyclopentadienyldiphenylsilyl group, an indenylmethylsilyl group, a di-n-butyl(indenyl)silyl group, an indenyl diphenylsilyl group, a fluorenyldimethylsilyl group, a di-n-butyl(fluorenyl)silyl group, a fluorenyldiphenylsilyl group, a 4-trimethylsilylphenyl group, a 4-triethylsilylphenyl group, a 4-tri-iso-propylsilylphenyl group, a 4-tert-butyldiphenylsilylphenyl group, a 4-triphenylsilylphenyl group, a 4-tris(trimethylsilyl)silylphenyl group, a 3,5-bis(trimethylsilyl)phenyl group, and the like.

[0062] Among the 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.

[0063] Examples of the oxygen-containing group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an allyloxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, a methallyloxy group, a prenyl-oxy group, a benzyloxy group, a methoxymethoxy group, a methoxyethoxy group, a phenoxy group, a naphthoxy group, a tolyloxy group, an iso-propylphenoxy group, an allylphenoxy group, a tert-butylphenoxy group, a methoxyphenoxy group, an iso-propoxyphenoxy group, an allyloxyphenoxy group, a biphenyloxy group, a binaphthyloxy group, a methoxymethyl group, an allyloxymethyl group, a benzyloxymethyl group, a phenoxymethyl group, a methoxyethyl group, an allyloxyethyl group, a benzyloxyethyl group, a phenoxyethyl group, a methoxypropyl group, an allyloxypropyl group, a benzyloxypropyl group, a phenoxypropyl group, a methoxyvinyl group, an allyloxyvinyl group, a benzyloxyvinyl group, a phenoxyvinyl group, a methoxyallyl group, an allyloxyallyl group, a benzyloxyallyl group, a phenoxyallyl group, a dimethoxymethyl group, a di-iso-propoxymethyl group, a dioxolanyl group, a tetramethyldioxolanyl group, a dioxanyl group, a 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 tetrahydrofuryl group, a pyranyl group, a tetrahydropyranyl group, a furofuryl group, a benzofuryl group, a dibenzofuryl group, and the like.

[0064] Among these oxygen-containing groups, alkoxy groups having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) are preferred. Specifically, methoxy group, ethoxy group, iso-propoxy group, allyloxy group, n-butoxy group, tert-butoxy group, prenyl-oxy group, benzyloxy group, phenoxy group, naphthoxy group, tolyloxy group, iso-propylphenoxy group, allylphenoxy group, tert-butylphenoxy group, methoxyphenoxy group, biphenyloxy group, binaphthyloxy group, allyloxymethyl group, benzyloxymethyl group, phenoxymethyl group, methoxyethyl group, methoxyallyl group, benzyloxyallyl group, phenoxyallyl group, dimethoxymethyl group, dioxolanyl group, tetramethyldioxolanyl group, dioxanyl group, dimethyldioxanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylenedioxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, tetrahydropyranyl group, furofuryl group, benzofuryl group, dibenzofuryl group, etc. are preferred, and methoxy group, iso-propoxy group, tert-butoxy group, allyloxy group, phenoxy group, dimethoxymethyl group, dioxolanyl group, methoxyphenyl group, iso-propoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, furyl group, methylfuryl group, benzofuryl group, dibenzofuryl group are more preferred.

[0065] Examples of the nitrogen-containing group include an amino group, dimethylamino group, diethylamino group, allylamino group, diallylamino group, didecylamino group, benzylamino group, dibenzylamino group, pyrrolidinyl group, piperidinyl group, morpholyl group, azepinyl group, dimethylaminomethyl group, dibenzylaminomethyl group, pyrrolidinylmethyl group, dimethylaminoethyl group, benzylaminomethyl group, benzylaminoethyl group, pyrrolidinylethyl group, dimethylaminovinyl group, benzylaminovinyl group, pyrrolidinylvinyl group, dimethylaminopropyl group, benzylaminopropyl group, pyrrolidinylpropyl group, dimethylaminoallyl group, benzylaminoallyl group, pyrrolidinylallyl group, aminophenyl group, dimethylaminophenyl group, 3,5-dimethyl-4-dimethylaminophenyl group, 3,5-di-iso-propyl-4-dimethylaminophenyl group, julolidinyl group, tetramethyldi julolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, pyridylphenyl group, quinolylphenyl group, isoquinolylphenyl group, indolinylphenyl group, indolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, methylpyrrolyl group, phenylpyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group, and the like.

[0066] Among these nitrogen-containing groups, amino groups having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) are preferred. Specifically, 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, tetramethyldulolidinyl group, pyrrolidinylphenyl group, pyrrolylphenyl group, carbazolylphenyl group, di-tert-butylcarbazolylphenyl group, pyrrolyl group, pyridyl group, quinolyl group, tetrahydroquinolyl group, iso-quinolyl group, tetrahydro-iso-quinolyl group, indolyl group, indolinyl group, carbazolyl group, di-tert-butylcarbazolyl group, imidazolyl group, dimethylimidazolidinyl group, benzimidazolyl group, oxazolyl group, oxazolidinyl group, benzoxazolyl group, etc. are preferred, 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, tetramethyldulolidinyl group, pyrrolidinylphenyl group, pyrrolyl group, pyridyl group, carbazolyl group, imidazolyl group are more preferred.

[0067] Examples of the sulfur-containing group include a methylthio group, an ethylthio group, a benzylthio group, a phenylthio group, a naphthylthio group, a methylthiomethyl group, a benzylthiomethyl group, a phenylthiomethyl group, a naphthylthiomethyl group, a methylthioethyl group, a benzylthioethyl group, a phenylthioethyl group, a naphthylthioethyl group, a methylthiovinyl group, a benzylthiovinyl group, a phenylthiovinyl group, a naphthylthiovinyl group, a methylthiopropyl group, a benzylthiopropyl group, a phenylthiopropyl group, a naphthylthiopropyl group, a methylthioallyl group, a benzylthioallyl group, a phenylthioallyl group, a naphthylthioallyl group, a mercaptophenyl group, a methylthiophenyl group, a thienylphenyl group, a methylthienylphenyl group, a benzothienylphenyl group, a dibenzothienylphenyl group, a benzodithienylphenyl group, a thienyl group, a tetrahydrothienyl group, a methylthienyl group, a thienofuryl group, a thienothienyl group, a benzothienyl group, a dibenzothienyl group, a thienobenzofuryl group, a benzodithienyl group, a dithiolanyl group, a dithianyl group, an oxathiolanyl group, an oxathianyl group, a thiazolyl group, a benzothiazolyl group, a thiazolidinyl group, and the like.

[0068] 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.

[0069] R 1 ~R 6 Among the adjacent substituents of R 1 and R 2 、R 2 and R 3 、R 3 and R 4 、R 4 and R 5 、and R 5 and R 6They may be bonded to 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 may have a substituent and is fused to the indenyl ring portion is preferable. When a plurality of rings exist, they may be the same 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 portion of the mother nucleus include a benzoindenyl ring, a tetrahydroindacenyl ring, and a tetrahydrobenzoindenyl ring (these may have a substituent), and a benzoindenyl ring and a tetrahydroindacenyl ring (these may have a substituent) are preferable.

[0070] R 7 ~R 12 Among the adjacent substituents of (for example, 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. 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 may have a substituent and is fused to the indenyl ring portion is preferable. When a plurality of rings exist, they may be the same 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 portion of the mother nucleus include a benzoindenyl ring, a tetrahydroindacenyl ring, a tetrahydrobenzoindenyl ring, a tetrahydrofluorenyl ring, and a fluorenyl ring (these may have a substituent), and a benzoindenyl ring and a tetrahydroindacenyl ring (these may have a substituent) are preferable.

[0071] R 13 and R 14 may be combined with each other to form a ring containing Q. In this case, the ring formed is preferably a 3- to 8-membered saturated or unsaturated ring which may have a substituent. Although not particularly limited as long as the effects of the present invention are achieved, the ring is preferably a 4- to 6-membered ring. In this case, R 13 and R 14 As the structure of Q combined with, for example, a substituted cyclobutane ring, a substituted cyclopentane ring, a substituted fluorene ring, a substituted silacyclobutane (siletane) ring, a substituted silacyclopentane (silolane) ring, a substituted silacyclohexane (silinane), a substituted silafluorene ring can be mentioned, and a substituted cyclopentane ring, a substituted silacyclobutane ring, a substituted silacyclopentane ring are preferred.

[0072] R 1 , R 2 , R 5 , R 6 , R 7 , R 8 , R 10 and R 11 are each independently preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, more preferably a hydrogen atom.

[0073] R 3 and R 4 are each independently preferably a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, more preferably a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms or a nitrogen-containing group having 1 to 20 carbon atoms, still more preferably a hydrocarbon group having 1 to 20 carbon atoms.

[0074] R 9 and R 12Each is independently, preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, more preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms or a nitrogen-containing group having 1 to 20 carbon atoms.

[0075] R 13 and R 14 Each is independently, preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, more preferably a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms or a nitrogen-containing group having 1 to 20 carbon atoms.

[0076] In addition, in R 7 the oxygen-containing group, nitrogen-containing group or sulfur-containing group may be a heterocyclic aromatic group described later. 《Preferred embodiments of transition metal compound [A]》 Preferred embodiments of the transition metal compound [A] include In the general formula [1], M is a zirconium atom or a hafnium atom, X is 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 is a carbon atom or a silicon atom, R 1 R 2 R 5 R 6 R 8 R 10 R 11 R 13 and R 14 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms (for example, an alkoxy group), a nitrogen-containing group having 1 to 20 carbon atoms (for example, an amino group) or a sulfur-containing group having 1 to 20 carbon atoms, R 3 and R 4is, independently of each other, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms, or a sulfur-containing group having 1 to 20 carbon atoms, and may combine with each other to form a ring which may have a substituent, 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 substituent which may have a substituent and contains at least one atom selected from nitrogen, oxygen, and sulfur in the heterocycle (for example, a furyl group or a thienyl group which may have a substituent), R 9 and R 12 are, independently of each other, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms (for example, an alkoxy group), a nitrogen-containing group having 1 to 20 carbon atoms (for example, an amino group), or a sulfur-containing group having 1 to 20 carbon atoms Examples of the transition metal compound [A-1] include.

[0077] A more preferred embodiment of the transition metal compound [A-1] is, In the general formula [1], Q is a silicon atom, R 1 、R 2 、R 5 、R 6 、R 8 、R 10 、R 11 、R 13 and R 14 are, independently of each other, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms, R 3 and R 4 are, independently of each other, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms, and may combine with each other to form a ring which may have a substituent, R 9 and R 12is, independently of each other, a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms or a nitrogen-containing group having 1 to 20 carbon atoms Examples of the transition metal compound [A-2] include

[0078] A more preferred embodiment of the transition metal compound [A-2] is a transition metal compound [A-3] in which R 1 and R 6 in the general formula [1] are hydrogen atoms. A more preferred embodiment of the transition metal compound [A-3] is a transition metal compound [A-4] in which R 2 and R 5 in the general formula [1] are hydrogen atoms.

[0079] A more preferred embodiment of the transition metal compound [A-4] is a transition metal compound [A-5] in which R 7 and R 8 in the general formula [1] are hydrogen atoms. A more preferred embodiment of the transition metal compound [A-5] is a transition metal compound [A-6] in which R 10 and R 11 in the general formula [1] are hydrogen atoms.

[0080] A more preferred embodiment of the transition metal compound [A-6] is a transition metal compound [A-7] in which at least one of R 3 and R 4 is a hydrocarbon group having 1 to 20 carbon atoms (when only one of R 3 and R 4 is a hydrocarbon group having 1 to 20 carbon atoms, the other one is a hydrogen atom).

[0081] A more preferred embodiment of the transition metal compound [A-7] is a transition metal compound in which R 3 and R 4Examples of the transition metal compound [A-8] include those in which each is independently a hydrocarbon group having 1 to 20 carbon atoms and may be bonded to each other to form a ring which may have a substituent.

[0082] A more preferred embodiment of the transition metal compound [A-7] or [A-8] is that in the general formula [1], R 9 Examples of the transition metal compound [A-9] include those in which is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 1 to 20 carbon atoms.

[0083] A more preferred embodiment of the transition metal compound [A-8] is that in the general formula [1], R 12 Examples of the transition metal compound [A-10] include those in which is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 1 to 20 carbon atoms.

[0084] In the transition metal compound [A], examples of the heterocyclic aromatic group which may have a substituent and has a 5-membered ring (hereinafter also referred to as "hetero 5-membered ring") as a mother skeleton containing at least one atom selected from the group consisting of nitrogen, oxygen and sulfur, which is one of R 7 include groups represented by the following general formulas [4a] to [4h].

[0085]

Chemical formula

[0086] In the general formulas [4a] to [4h], Ch is an oxygen atom or a sulfur atom, and R d are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different from each other.

[0087] The wavy lines in the general formulas [4a] to [4h] indicate the bonding sites with the indenyl ring. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the above-described R 1 ~R 14Among the examples of the hydrocarbon group having 1 to 40 carbon atoms as described above, those having 1 to 20 carbon atoms are mentioned. Preferably, methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, iso-pentyl group, neopentyl group, tert-pentyl group, allyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctenyl group, norbornyl group, bicyclo[2.2.2]octan-1-yl group, 1-adamantyl group, 2-adamantyl group, benzyl group, benzhydryl group, cumyl group, 1,1-diphenylethyl group, trityl group, 2-phenylethyl group, 3-phenylpropyl group, cinnamyl group, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4-adamantylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, phenanthryl group, anthracenyl group, ferrocenyl group are mentioned. More preferably, methyl group, ethyl group, 1-propyl group, 1-butyl group, iso-propyl group, sec-butyl group, tert-butyl group, iso-butyl group, allyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, benzyl group, phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, biphenyl group, terphenyl group are mentioned.

[0088] R d are each independently an adjacent R dThey may be bonded to each other to form a saturated or unsaturated hydrocarbon group which, together with the atoms of the heterocyclic 5-membered ring moiety, may be fused to the heterocyclic 5-membered ring moiety to form a 5- to 8-membered ring. The 5- to 8-membered ring is not particularly limited as long as the effects of the present invention are achieved, but is preferably a 5- or 6-membered ring. In this case, as a structure combining this ring and the heterocyclic 5-membered ring moiety of the parent nucleus, for example, a benzofuran ring, a benzothiophene ring, an indole ring, a carbazole ring, a benzoxazole ring, a benzothiazole ring, a benzimidazole ring, a benzopyrazole ring, etc. can be mentioned.

[0089] Among the heterocyclic aromatic groups represented by the general formulas [4a] to [4h], the heterocyclic aromatic group represented by the general formula [4a] is preferred. Among the heterocyclic aromatic groups represented by the general formula [4a], a 2-furyl group, a 5-methyl-2-furyl group, a 2-thienyl group, and a 5-methyl-2-thienyl group are preferred.

[0090] 《Examples of transition metal compound [A]》 Specific examples of the transition metal compound [A] are shown below, but the scope of the present invention is not particularly limited thereby.

[0091] For convenience, the ligand structure excluding the portion represented by MXn (metal portion) of the transition metal compound [A] is divided into seven structures of a 2-indenyl ring portion, a 1-indenyl ring portion, an indenyl ring portion R 1 , R 6 and R 8 substituents, an indenyl ring portion R 2 , R 5 , R 9 and R 12 substituents, an indenyl ring portion R 3 , R 4 , R 10 and R 11 substituents, a 1-indenyl ring portion R 7 substituents, and the structure of the bridging portion. The abbreviation of the 2-indenyl ring portion is α, the abbreviation of the 1-indenyl ring portion is β, the indenyl ring portion R 1 , R 6 and R 8The abbreviation of the substituent is γ, and the indenyl ring moiety R 2 、R 5 、R 9 、and R 12 The abbreviation of the substituent is δ, and the indenyl ring moiety R 3 、R 4 、R 19 、and R 11 The abbreviation of the substituent is ε, and the 1-indenyl ring moiety R 7 The abbreviation of the substituent is ζ, the abbreviation of the structure of the crosslinked moiety is η, and the abbreviations of each substituent are shown in [Table 1] to [Table 7].

[0092]

Table 1

[0093]

Table 2

[0094] Note that the wavy lines in the above [Table 1] to [Table 2] indicate the bonding sites to the crosslinked moiety.

[0095]

Table 3

[0096] The R 1 、R 6 and R 8 substituents in the above [Table 3] may be the same or different from each other in their combinations.

[0097]

Table 4

[0098] The R 2 、R 5 、R 9 、and R 12 substituents in the above [Table 4] may be the same or different from each other in their combinations. However, the R 9 substituent isIt will not be δ-20 to δ-54.

[0099]

Table 5

[0100] R in the above [Table 5] 3 、R 4 、R 10 、and R 11 substituents may be the same as or different from each other in their combination. However, the substituents of R 3 、R 4 will not be ε-1.

[0101]

Table 6

[0102]

Table 7

[0103] 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.

[0104] According to the above notation, the 2-indenyl ring moiety is α-3 in [Table 1], the 1-indenyl ring moiety is β-1 in [Table 2], and the indenyl ring moieties R 1 、R 6 and R 8 substituents are all γ-1 in [Table 3], the 2-indenyl ring moieties R 2 and R 5When all the substituents are δ-1 in [Table 4], 1-indenyl ring moiety R 7 When the substituent is ζ-30 in [Table 6], 1-indenyl ring moiety R 9 When the substituent is δ-2 in [Table 4], 1-indenyl ring moiety R 12 When the substituent is δ-3 in [Table 4] and the bridging moiety is η-20 in [Table 7], and when MXn of the metal moiety is ZrCl2, the compounds represented by the following formula [5] are exemplified.

[0105]

Chemical formula

[0106] Also, when the 2-indenyl ring moiety is α-3 in [Table 1], the 1-indenyl ring moiety is β-1 in [Table 2], indenyl ring moiety R 1 , R 6 and R 8 When all the substituents are γ-1 in [Table 3], indenyl ring moiety R 2 , R 5 , R 9 and R 12 When all the substituents are δ-2 in [Table 4], indenyl ring moiety R 10 and R 11 When all the substituents are ε-1 in [Table 5], 1-indenyl ring moiety R 7 When the substituent is ζ-2 in [Table 6] and the bridging moiety is η-20 in [Table 7], and when MXn of the metal moiety is ZrCl2, the compounds represented by the following formula [6] are exemplified.

[0107]

Chemical formula

[0108] Also, when the 2-indenyl ring moiety is α-3 in [Table 1], the 1-indenyl ring moiety is β-1 in [Table 2], 2-indenyl ring moiety R 1 and R 6 When all the substituents are γ-2 in [Table 3], 2-indenyl ring moiety R 2 and R 5All the substituents are δ-1 in [Table 4], 1-indenyl ring moiety R 7 The substituents are ζ-12 in [Table 6], 1-indenyl ring moiety R 8 The substituents are γ-1 in [Table 3], 1-indenyl ring moiety R 9 The substituents are δ-4 in [Table 4], 1-indenyl ring moiety R 10 The substituents are ε-1 in [Table 5], 1-indenyl ring moiety R 11 The substituents are ε-12 in [Table 5], 1-indenyl ring moiety R 12 When the substituents are δ-3 in [Table 4], the bridging moiety is η-31 in [Table 7], and MXn of the metal moiety is HfMe2, the following compound represented by formula [7] is exemplified.

[0109]

Chemical formula

[0110] Also, the 2-indenyl ring moiety is α-1 in [Table 1], the 1-indenyl ring moiety is β-1 in [Table 2], 2-indenyl ring moiety R 1 and R 6 All the substituents are γ-1 in [Table 3], 2-indenyl ring moiety R 2 and R 5 The substituents are δ-1 in [Table 4], 2-indenyl ring moiety R 3 and R 4 The substituents are ε-2 in [Table 5], 1-indenyl ring moiety R 10 and R 11 The substituents are ε-1 in [Table 5], 1-indenyl ring moiety R 7 The substituents are ζ-1 in [Table 6], 1-indenyl ring moiety R 8 The substituents are γ-9 in [Table 3], 1-indenyl ring moiety R 9 The substituents are δ-5 in [Table 4], R 12 When the substituents are δ-22 in [Table 4], the bridging moiety is η-4 in [Table 7], and MXn of the metal moiety is Ti(1,3-pentadienyl), the following compound represented by formula [8] is exemplified.

[0111]

Chemical formula

[0112] Further, in the transition metal compound [A], there are two directions in which the planes of the indenyl ring moieties that are bonded to the central metal with the bridging 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 exist, for example, two types of structural isomers represented by the following general formula [9a] or [9b].

[0113] [Chemical formula]

[0114] Similarly, when the substituents R 13 and R 14 of the bridging moiety are not the same, there exist, for example, two types of structural isomers represented by the following general formula [10a] or [10b].

[0115] [Chemical formula]

[0116] Purification, separation, or selective production of these structural isomer mixtures is possible by known methods, and in particular, the production method is not limited. Known production methods include, in addition to those mentioned as the production method of the transition metal compound [A], the production methods disclosed in JP-A-10-109996, "Organometallics 1999, 18, 5347.", "Organometallics 2012, 31, 4340.", JP-T-2011-502192, and the like.

[0117] Within the range of the transition metal compound [A], the transition metal compound may be used alone, two or more thereof may be used in combination, a mixture of structural isomers may be used, a structural isomer may be used alone, or a mixture of two or more structural isomers may be used. Further, within a range where the effects of the present invention are not impaired, one or more transition metal compounds different from the transition metal compound [A] may be used in combination. At this time, the transition metal compound [A] may be in any of the above-described embodiments.

[0118] 《Production Method of Transition Metal Compound [A]》 The transition metal compound [A] can be produced by using a conventionally known method, for example, the method described in

[0097] to

[0115] of JP-A-2019-59933 or the method described in

[0098] to

[0116] of JP-A-2019-59724, where R 1 ~R 14 , Q, M, X, and n are read as having the same meanings as those described in the above general formula [1].

[0119] [Catalyst for olefin polymerization] The olefin polymerization catalyst of the present invention contains the transition metal compound [A] of the present invention. Typical examples of the olefin polymerization catalyst of the present invention include an ethylene polymerization catalyst.

[0120] (Compound [B]) The olefin polymerization catalyst of the present invention preferably further contains [B-1] an organometallic compound, preferably an organometallic compound represented by the following general formula (B-1a), (B-1b), or (B-1c) (hereinafter also referred to as "component (B-1)"). R a m Al(OR b ) n H p X q … (B-1a) 〔In the general formula (B-1a), R a and R brepresents a hydrocarbon group having 1 to 15 carbon atoms, which may be the same as or different from each other, X represents a halogen atom, m satisfies 0 < m ≦ 3, n satisfies 0 ≦ n <3, p satisfies 0 ≦ p < 3, q satisfies 0 ≦ q < 3, and m + n + p + q = 3.]] M a AlR a 4…(B-1b) 〔In the general formula (B-1b), M a represents Li, Na or K, and R a represents a hydrocarbon group having 1 to 15 carbon atoms.〕 R a r M b R b s X t …(B-1c) 〔In the general formula (B-1c), R a and R b represent hydrocarbon groups having 1 to 15 carbon atoms, which may be the same as or different from each other, 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.〕 [B-2] An organoaluminum oxy compound (hereinafter also referred to as "component (B-2)"), and [B-3] At least one compound [B] selected from the group consisting of a compound that reacts with the transition metal compound (A) to form an ion pair (hereinafter also referred to as "component (B-3)") is included. (Hereinafter, it may also be referred to as "component (B)".)

[0121] As the organometallic compound [B-1], the compounds disclosed in JP-A-11-315109 or EP0874005A can be used without limitation. As the organometallic compound [B-1], those represented by the general formula (B-1a) are preferable. Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; 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.

[0122] These are used singly or in combination of two or more. As the organoaluminum oxy compound [B-2], an aluminoxane prepared from trialkylaluminum or tricycloalkylaluminum is preferable, and an organoaluminum oxy compound prepared from trimethylaluminum or triisobutylaluminum is particularly preferable. Such an organoaluminum oxy compound is used singly or in combination of two or more.

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

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

[0125] (Solid carrier [S]) The olefin polymerization catalyst of the present invention preferably contains a solid carrier [S] (hereinafter sometimes referred to as "carrier [S]" or "component (S)").

[0126] The solid carrier [S] is an inorganic compound or an organic compound and is a granular or particulate solid. As the inorganic compound, a porous oxide, a solid aluminoxane compound, an inorganic halide, clay, a clay mineral, or an ion-exchangeable layered compound is preferable.

[0127] As the porous oxide, specifically, SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc., or a composite or mixture containing these can be used. Further, for example, natural or synthetic zeolite, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc. can be used. Among these, those having SiO2 and / or Al2O3 as the main component are preferable as the porous oxide.

[0128] The porous oxide may contain a small amount of carbonate, sulfate, nitrate, oxide components such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, Li2O.

[0129] Although the properties of the porous oxide vary depending on the type and production method, the porous oxide preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m 2 / g, preferably 100 to 700 m 2 / g, and a pore volume in the range of 0.3 to 3.0 cm 3 / g. Such a porous oxide is used after being calcined at 100 to 1000 °C, preferably 150 to 700 °C as necessary.

[0130] Examples of the solid aluminoxane compound include at least one aluminoxane selected from aluminoxanes having a structure represented by the following general formula (S-a) or (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).

[0131]

Chemical formula

[0132] In the general formulas (S-a) to (S-d), R e is, independently of one another, a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and specific examples thereof include hydrocarbon groups such as methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, cyclohexyl group, cyclooctyl group, phenyl group, tolyl group, ethylphenyl group, etc., and a methyl group, an ethyl group, and an isobutyl group are preferred, and a methyl group is particularly preferred. Also, R e may be partially substituted with a halogen atom such as chlorine or bromine, and the halogen content may be 40% by weight or less based on R e . One of the straight lines not connected to an atom in (S-c) and (S-d) indicates a bond with another atom not shown in the drawing.

[0133] In the general formulas (S-a) and (S-b), r represents an integer of 2 to 500, preferably in the range of 6 to 300, particularly preferably 10 to 100. In the general 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.

[0134] The solid aluminoxane compound does not contain an inorganic solid component such as silica or alumina or an organic polymer component such as polyethylene or polystyrene, unlike a conventionally known carrier for an olefin polymerization catalyst, and is a solidified product mainly composed of 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 below, and when performing 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.

[0135] Whether the aluminoxane component is in a solid state or not 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 preferred. 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.

[0136] 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%.

[0137] 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.

[0138] 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.

[0139] The average particle diameter of the solid aluminoxane compound is generally in the range of 0.01 to 50000 μm, preferably 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 of each particle is measured by sandwiching the particle image with two parallel lines in the horizontal and vertical directions and measuring the length, and is determined by the following formula.

[0140] Particle diameter = ((Horizontal length 2 + Vertical length 2 ) 0.5 Next, the weight average particle diameter of the solid aluminoxane compound is determined by the following formula using the particle diameter obtained above.

[0141] Weight average particle diameter = Σnd 4 / Σnd 3 (n; number of particles, d; particle diameter) 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, which is desirable.

[0142] As the inorganic halide, MgCl2, MgBr2, MnCl2, MnBr2, etc. are used. The inorganic halide may be used as it is as obtained, or may be used after being pulverized by a ball mill or a vibration mill. Also, after dissolving the inorganic halide in a solvent such as alcohol, a precipitate obtained by precipitation into fine particles with a precipitating agent can also be used.

[0143] The clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds or the like are stacked parallel to each other with a weak binding force, and the contained ions are exchangeable. Most clay minerals are ion-exchangeable layered compounds. Also, as these clays, clay minerals, and ion-exchangeable layered compounds, not limited to natural products, synthetic products can also be used.

[0144] Examples of the clay, clay mineral, or ion-exchangeable layered compound include ion-crystalline compounds having a layered crystal structure such as a hexagonal close-packed type, an antimony type, a CdCl2 type, and a CdI2 type.

[0145] Furthermore, examples of the clay and clay mineral 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.

[0146] Such clays, clay minerals or ion-exchangeable layered compounds preferably have a pore volume of 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g, for pores with a radius of 20 Å or more measured by the mercury intrusion method. Here, the pore volume is measured in the range of pore radii of 20 to 30,000 Å by the mercury intrusion method using a mercury porosimeter.

[0147] When a carrier having a pore volume of less than 0.1 cc / g for pores with a radius of 20 Å or more is used, it tends to be difficult to obtain high polymerization activity. It is also preferable to subject the above-mentioned clays and clay minerals to chemical treatment. As the chemical treatment, any treatment such as a surface treatment for removing impurities adhering to the surface and a treatment that affects the crystal structure of the clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment not only removes surface impurities but also increases the surface area by eluting cations such as Al, Fe, and Mg 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, and the surface area and interlayer distance can be changed.

[0148] 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. Guest compounds for intercalation include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (where R is a hydrocarbon group, etc.), [Al 13 O4(OH) 24 7+ 、[Zr4(OH) 14 2+ 、[Fe3O(OCOCH3)6] + ​​Examples include metal hydroxide ions such as etc. 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 represents a hydrocarbon group etc.), colloidal inorganic compounds such as SiO2, etc. can also coexist. Also, as the pillars, oxides formed by heating and dehydrating after intercalating the above metal hydroxide ions between the layers can also be mentioned.

[0149] The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as obtained, or may be used after treatments such as ball milling and sieving. Also, it may be used after newly adsorbing water or after heat dehydration treatment. Further, it may be used alone or in combination of two or more.

[0150] Among these, preferred ones are clay or clay minerals, and particularly preferred ones are montmorillonite, vermiculite, peclolite, teniolite, and synthetic mica. Examples of the organic compound that can be used as the carrier [S] include granular or fine particulate solids having a particle size in the range of 1 to 300 μm. Specifically, polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, polymers produced mainly from vinylcyclohexane or styrene, and modified products thereof can be exemplified.

[0151] <Usage method and addition order of each component> The olefin polymerization catalyst according to the present invention can be prepared by mixing and contacting component (A), optionally component (S), and optionally component (B) in an inert hydrocarbon.

[0152] As a method of contacting each component, paying attention to the order of contact, for example, (i) A method of bringing component (B) into contact with component (A) (ii) A method of bringing component (A) into contact with component (S) (iii) A method of bringing component (B) into contact with component (S), and then bringing component (A) into contact therewith (iv) A method of bringing component (B) into contact with component (A), and then bringing component (S) into contact therewith (v) A method of bringing component (B) into contact with component (S), and then bringing a mixture of component (A) and component (B) into contact therewith (vi) A method of bringing component (B) into contact with component (S), further bringing component (B) into contact therewith, and then bringing a mixture of component (A) and component (B) into contact therewith etc. When a plurality of types of component (B) are used, the component (B)'s may be the same or different from each other. Among the above methods, (i), (ii), (iii) and (iv) are preferred.

[0153] In each of the methods showing the above contact order forms, in the step including the contact between component (S) and component (B) and the step including the contact between component (S) and component (A), by co-existing component (G), fouling during the polymerization reaction is suppressed or the particle properties of the produced polymer are improved. As component (G), a compound having a polar functional group can be used, a nonionic surfactant is preferred, and a polyalkylene oxide block, a higher aliphatic amide, a polyalkylene oxide, a polyalkylene oxide alkyl ether, an alkyldiethanolamine, a polyoxyalkylene alkylamine, a glycerin fatty acid ester, an N-acyl amino acid are more preferred. These may be used alone or in combination of two or more.

[0154] Examples of the solvent used for preparing the olefin polymerization catalyst according to the present invention 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; or mixtures thereof. Depending on the type of olefin to be polymerized, the olefin itself can also be used as a solvent.

[0155] In the contact between component (B) and component (S), they are chemically bonded by the reaction between the reaction sites in component (B) and the reaction sites in component (S), and a contact product of component (B) and component (S) is formed. The contact time between component (B) and component (S) is usually 1 minute to 20 hours, preferably 30 minutes to 10 hours, and the contact temperature is usually -50 to 200°C, preferably -20 to 120°C. If the initial contact between component (B) and component (S) is carried out abruptly, component (S) may disintegrate due to the heat of reaction and reaction energy, deteriorating the morphology of the resulting solid catalyst component. When this is used in polymerization, continuous operation is often difficult due to poor polymer morphology. Therefore, at the initial stage of contact between component (B) and component (S), for the purpose of suppressing the heat of reaction, it is preferable to contact at a lower temperature, or to control the heat of reaction and react at a rate capable of maintaining the initial contact temperature. The same applies when component (B) and component (S) are contacted and then component (B) is contacted again. The contact weight ratio of component (B) to component (S) [= weight of component (B) / weight of component (S)] can be arbitrarily selected, but the higher the contact weight ratio, the more component (A) can be contacted, and the catalytic activity per unit weight of the solid catalyst component can be improved.

[0156] The contact weight ratio of component (B) to component (S) [= weight of component (B) / weight of component (S)] is preferably 0.05 to 3.0, particularly preferably 0.1 to 2.0. When bringing the contact product of component (B) and component (S) into contact with component (A), the contact time is usually 1 minute to 20 hours, preferably 1 minute to 10 hours, and the contact temperature is usually in the range of -50 to 200 °C, preferably -50 to 100 °C.

[0157] Component (B-1) is used in an amount such that the molar ratio [(B-1) / M] of component (B-1) to all transition metal atoms (M) in component (A) is usually 0.01 to 100,000, preferably 0.05 to 50,000.

[0158] Component (B-2) is used in an amount such that the molar ratio [(B-2) / M] of component (B-2) (in terms of aluminum atoms) to all transition metal atoms (M) in component (A) is usually 10 to 500,000, preferably 20 to 100,000.

[0159] Component (B-3) is used in an amount such that the molar ratio [(B-3) / M] of component (B-3) to all transition metal atoms (M) in component (A) is usually 1 to 10, preferably 1 to 5. The ratio of component (B) to all transition metal atoms (M) in component (A) can be determined by inductively coupled plasma optical emission spectrometry (ICP spectrometry).

[0160] For olefin polymerization, the olefin polymerization catalyst according to the present invention can be used as it is, or it can also be used after prepolymerizing an olefin with this olefin polymerization catalyst to form a prepolymerized solid catalyst component.

[0161] The prepolymerized solid catalyst component can usually be prepared by prepolymerizing an olefin (e.g., ethylene) etc. in an inert hydrocarbon solvent in the presence of the olefin polymerization catalyst according to the present invention, and it can be carried out by any of batch, semi-continuous, and continuous methods, and can also be carried out under reduced pressure, normal pressure, or increased pressure. Further, it is desirable that the prepolymerized solid catalyst component is produced in an amount of 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g per 1 g of the solid catalyst component by prepolymerization.

[0162] After separating the prepolymerized solid catalyst component formed in an inert hydrocarbon solvent from the suspension, it may be resuspended in an inert hydrocarbon again, and an olefin (e.g., ethylene) may be introduced into the resulting suspension, or an olefin (e.g., ethylene) may be introduced after drying.

[0163] The prepolymerization temperature is -20 to 80 °C, preferably 0 to 60 °C, and the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 50 hours. For prepolymerization, an olefin mainly composed of ethylene is preferably used.

[0164] As the form of the solid catalyst component used for prepolymerization, those already described can be used without limitation. Further, component (B) is used as necessary, and in particular, an organoaluminum compound [B-1a] represented by the general formula (B-1a) is preferably used. When component (B) is used, component (B) is used in an amount such that the molar ratio (Al / M) of the aluminum atom (Al) in component (B) to the transition metal atom (M) in the transition metal compound [A] is 0.1 to 10,000, preferably 0.5 to 5,000.

[0165] The concentration of the olefin polymerization catalyst according to the present invention in the prepolymerization system is preferably 1 to 1,000 grams / liter, more preferably 10 to 500 grams / liter, in terms of the olefin polymerization catalyst / polymerization volume ratio. During prepolymerization, component (G) may coexist for the purpose of suppressing fouling or improving the particle properties.

[0166] Further, for the purpose of improving the fluidity of the prepolymerized solid catalyst component, heat spot seating during polymerization, and suppressing the generation of polymer lumps, component (G) may be brought into contact with the prepolymerized solid catalyst component once formed by prepolymerization.

[0167] The temperature when bringing component (G) into contact is usually -50 to 50 °C, preferably -20 to 50 °C, and the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 10 hours. When bringing the olefin polymerization catalyst according to the present invention into contact with component (G), component (G) is used in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.4 to 5 parts by weight, based on 100 parts by weight of the olefin polymerization catalyst according to the present invention.

[0168] The mixing contact between the olefin polymerization catalyst according to the present invention and component (G) can be carried out in an inert hydrocarbon solvent, and examples of the inert hydrocarbon solvent include the same ones as described above. In the method for producing an olefin polymer according to the present invention, as the olefin polymerization catalyst, a dried prepolymerized solid catalyst component (hereinafter also referred to as "dried prepolymerized catalyst") can be used. The drying of the prepolymerized solid catalyst component is usually carried out after removing the hydrocarbon as the dispersion medium by filtration or the like from the obtained suspension of the prepolymerized catalyst.

[0169] The drying of the prepolymerized solid catalyst component is carried out by maintaining the prepolymerized solid catalyst component 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 prepolymerized catalyst is 2.0% by weight or less, preferably 1.0% by weight or less. The lower the volatile component content of the dried prepolymerized catalyst, the better, and although there is no particular lower limit, it is practically 0.001% by weight. The drying time is usually 1 to 48 hours, depending on the drying temperature.

[0170] Since the dried prepolymerized catalyst has excellent fluidity, it can be stably supplied to the polymerization reactor. Further, when the dried prepolymerized catalyst is used, polymerization can be carried out stably because it is not necessary to entrain the solvent used in suspension in the gas-phase polymerization system.

[0171] [Method for producing olefin polymer] The method for producing an olefin polymer of the present invention is characterized by polymerizing an olefin in the presence of the olefin polymerization catalyst of the present invention.

[0172] As a preferred embodiment of the method for producing an olefin polymer of the present invention, a method for producing an ethylene-based polymer can be mentioned. In this method, ethylene is polymerized or ethylene and an olefin having 3 to 20 carbon atoms are polymerized in the presence of the olefin polymerization catalyst of the present invention.

[0173] When the method for producing an olefin polymer of the present invention is a method for producing an ethylene-based polymer, the ethylene content in the ethylene-based polymer is preferably 70 mol% or more (assuming the total of monomer units is 100 mol%).

[0174] Examples of the polymerization method include liquid phase polymerization methods such as solution polymerization and suspension polymerization, and gas phase polymerization methods. Suspension polymerization methods and gas phase polymerization methods are preferred. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof.

[0175] When carrying out the polymerization of an olefin (e.g., ethylene) using the olefin polymerization catalyst according to the present invention, component (A) is usually 1×10 -12 ~1×10 -1 mol, preferably 1×10 -8 ~1×10 -2 mol, per liter of reaction volume. Further, component (B) is used, preferably a compound represented by the general formula (B-1a), or component (B-2) is used.

[0176] When polymerizing an olefin (e.g., ethylene), the lower limit of the polymerization temperature is 0°C, preferably 40°C, particularly preferably 60°C. A higher temperature is advantageous in terms of heat removal etc. in industrial scale production. The upper limit is usually 200°C, preferably 170°C, and the polymerization pressure is usually from atmospheric pressure to 100 kgf / cm 2, preferably normal pressure to 50 kgf / cm 2 is.

[0177] The polymerization reaction can be carried out by any of the batch, semi - continuous, and continuous methods. Further, it is also possible to carry out the polymerization in two or more stages with different reaction conditions. The molecular weight of the olefin polymer obtained by the method for producing an olefin polymer according to the present invention can be adjusted by causing hydrogen to be present in the polymerization system or by changing the polymerization temperature. During polymerization, the component (G) can be co - present for the purpose of suppressing fouling or improving the particle properties.

[0178] When the method for producing an olefin polymer of the present invention is a method for producing an ethylene - based polymer, the monomer supplied to the polymerization reaction is ethylene alone or ethylene and an olefin having 3 to 20 carbon atoms. Specific examples of the olefin having 3 to 20 carbon atoms include α - olefins such as propylene, 1 - butene, 1 - pentene, 1 - hexene, 4 - methyl - 1 - pentene, 1 - octene, 1 - decene, 1 - dodecene, 1 - tetradecene, 1 - hexadecene, 1 - octadecene, 1 - eicosene, and 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.

[0179] Furthermore, in a range that does not impair the effects of the present invention, a small amount of styrene, vinylcyclohexane, diene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, etc.; polar monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid, etc. may be supplied.

[0180] According to the method for producing an olefin polymer according to the present invention, since the transition metal compound [A] easily causes β-hydrogen elimination due to the β-agostic interaction with the growing polymer chain, it is presumed that an olefin polymer (especially an ethylene-based polymer) containing many molecular chains having a vinyl group at the terminal and having a low molecular weight can be produced with high polymerization activity.

[0181] [Olefin polymer] The olefin polymer (e.g., ethylene-based polymer) produced by the present invention may be pelletized.

[0182] Additives such as a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-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 may be blended as necessary in the olefin polymer (e.g., ethylene-based polymer) produced by the present invention within a range not impairing the object of the present invention.

[0183] The olefin polymer (e.g., ethylene-based polymer) produced by the present invention can be processed by general film forming, blow molding, injection molding, and extrusion molding. Examples of the molded article obtained by processing the olefin polymer (e.g., ethylene-based polymer) produced by the present invention include films, blow infusion bags, blow bottles, gasoline tanks, tubes by extrusion molding, pipes, tear-off caps, injection molded articles such as daily sundries, fibers, and large molded articles by rotational molding.

[0184] The film obtained by processing the olefin polymer (e.g., ethylene-based polymer) produced by the present invention is suitable for various packaging films such as water product packaging bags, liquid soup packaging bags, liquid paper containers, laminated base materials, special-shaped liquid packaging bags (such as standing pouches), standard bags, heavy bags, wrap films, sugar bags, oil product packaging bags, food packaging, protective films, infusion bags, agricultural materials, etc., and can also be used as a multilayer film by laminating with a base material such as nylon or polyester.

Examples

[0185] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. [Measurement of various physical properties] A method for measuring the physical properties of an ethylene-based polymer is shown below.

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

[0187] <Number average molecular weight (Mn), weight average molecular weight (Mw), Z average molecular weight (Mz), molecular weight distribution (Mw / Mn, Mz / Mw)> Using a GPC-viscosity detector (GPC-VISCO) PL-GPC220 manufactured by Agilent, the measurement was performed as follows.

[0188] Two Agilent PLgel Olexis were used as analysis columns, a differential refractometer and a 3-capillary viscometer were used as detectors, the column temperature was 145 °C, o-dichlorobenzene was used as the mobile phase, the flow rate was 1.0 ml / min, and the sample concentration was 0.1 wt%. Standard polystyrene 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.

[0189] <Terminal vinyl ratio> The terminal vinyl ratio (%) of the olefin polymer was calculated by the following formula from the number average molecular weight (Mn) and the number of vinyl terminals (α) per 1000 main chain methylene carbons. The number of vinyl terminals (α) per 1000 main chain methylene carbons was 1 Determined using 1H-NMR (ECA-500 manufactured by JEOL Ltd.).

[0190] Vinyl ratio at the terminal of the olefin polymer (%) = Number average molecular weight (Mn) × (Number of vinyl terminals per 1000 main-chain methylenes (α)) / 14000 (equivalent to the molecular weight of 1000 main-chain methylenes) × 100 <Synthesis of transition metal compound (A)> [Synthesis Example 1-1] 1.46 g (60.0 mmol) of magnesium chips were charged into a 200 mL reactor that had been thoroughly dried and purged with argon, and the mixture was vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and one piece of iodine and 20 mL of tetrahydrofuran were charged and stirred. Further, a diluted solution of 3.53 g (15.0 mmol) of 6-bromo-1,2,3,5-tetrahydro-s-indacene synthesized by the method of Example 5 of JP-A-2001-253895 in 20 mL of tetrahydrofuran was added dropwise (after adding 1.0 mL, heated to reflux with a dryer until the color of iodine disappeared, and the remaining solution was added dropwise after the start of the reaction), and after completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. This reaction solution was slowly added to a diluted solution of 9.00 mL (75.3 mmol) of dimethylsilyl dichloride in 15 mL of n-hexane while cooling at -78 °C, and stirring was continued for 19 hours while returning to room temperature. After distilling off the solvent of the reaction solution and unreacted dimethylsilyl dichloride, 10 mL of tetrahydrofuran and 1.62 mL (15.0 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue to obtain Solution 1a.

[0191] 2.16 g (15.0 mmol) of 4,7-dimethyl-1H-indene and 15 mL of tetrahydrofuran were charged into a 100 mL reactor that had been thoroughly dried and purged with argon, 10.2 mL of an n-butyllithium solution (hexane solution, 1.55 M, 15.8 mmol) was added, and the mixture was stirred at room temperature for 2 hours to obtain Solution 1b.

[0192] This solution 1b was added dropwise to solution 1a cooled to -78 °C, and stirring was continued for 15 hours while slowly returning to room temperature. An aqueous saturated ammonium chloride solution was added, the soluble components were extracted with hexane, the resulting fraction was washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography to obtain 3.36 g (yield 62%) of the target product (hereinafter referred to as "compound (A-1L)") as a mixture of isomers represented by the following formula (A-1L). 1 H NMR (270 MHz, CDCl3) δ 7.31 (1H, s, Ar-H), 7.23 (1H, s, Ar-H), 7.02 (1H, m, Ar-H), 6.96 - 6.93 (2H, m, Ar-H, C=CH-C), 6.87 - 6.84 (1H, m, C=CH-C), 6.63 - 6.61 (1H, dd, J = 5.4 and 1.9 Hz, C=CH-C), 3.82 (1H, m, Si-CH), 3.28 (2H, s, Ar-CH2-C), 2.95 - 2.89 (4H, t, J = 14.8 Hz, Ar-CH2-CH2), 2.41 (3H, s, -CH3), 2.21 (3H, s, -CH3), 2.15 - 2.05 (2H, m, CH2-CH2-CH2), 0.08 (3H, s, Si-CH3), 0.07 (3H, s, Si-CH3) ppm

[0193]

Chemical formula

[0194] 〔Example 1A〕 0.72 g (2.00 mmol) of the compound (A-1L) obtained in Synthesis Example 1-1, 20 mL of toluene, and 0.4 mL of tetrahydrofuran were charged into a sufficiently dried and argon-substituted 100 mL reactor and stirred. To the solution thus obtained, 2.58 mL of an n-butyllithium solution (hexane solution, 1.55 M, 4.00 mmol) was added at room temperature, and then stirring was continued in an oil bath at 40 °C for 3 hours. This solution was cooled to 0 °C, 0.47 g (2.00 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and insoluble matters were removed with celite on a glass filter. After concentrating the obtained solution under reduced pressure, a suspension was prepared by adding n-hexane, insoluble matters were filtered off with a glass filter, and the residue was dried under reduced pressure to obtain 0.55 g (yield 53%) of a yellow powdery compound (dimethylsilylene(1,5,6,7-tetrahydro-s-2-indacenyl)(4,7-dimethyl-1-indenyl)zirconium dichloride, hereinafter referred to as "transition metal compound (A-1)") represented by the following formula (A-1). 1 H NMR (270 MHz, CDCl3) δ 7.33 (1H, s, Ar-H), 7.22 (1H, s, Ar-H), 7.07 - 7.06 (1H, d, J = 3.7 Hz, Ar-H), 6.99 - 6.87 (2H, m, Ar-H), 6.39 - 6.38 (1H, d, J = 3.5 Hz, Ind-H), 6.00 - 5.99 (1H, d, J = 1.8 Hz, Ind-H), 5.88 - 5.88 (1H, d, Ind-H), 2.95 - 2.86 (4H, m, Ar-CH2-CH2), -2.56 (3H, s, -CH3), 2.37 (3H, s, -CH3), 2.09 - 1.98 (2H, m, CH2-CH2-CH2), 1.05 (3H, s, Si-CH3), 0.91 (3H, s, Si-CH3) ppm FD-mass spectrometry (M + ): 514

[0195]

Chemical formula

[0196] [Synthesis Example 2-1] In a sufficiently dried and argon-substituted 200 mL reactor, 1.46 g (60.0 mmol) of magnesium chips were charged, and the mixture was vigorously stirred for 30 minutes while heating under reduced pressure. After cooling to room temperature, a reflux condenser was attached, and one piece of iodine and 15 mL of tetrahydrofuran were charged and stirred. Further, a diluted solution of 3.35 g (15.0 mmol) of 2-bromo-5,6-dimethyl-1H-indene synthesized by the method described on pages 9 to 10 of WO 2000 / 035975 in 20 mL of tetrahydrofuran was added dropwise (after adding 1.0 mL, heated to reflux with a dryer until the color of iodine disappeared, and the remaining solution was added dropwise after the start of the reaction). After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. This reaction solution was slowly added to a diluted solution of 8.96 mL (75.0 mmol) of dimethylsilyl dichloride in 10 mL of n-hexane while cooling at -78 °C, and stirring was continued for 19 hours while returning to room temperature. After distilling off the solvent of the reaction solution and unreacted dimethylsilyl dichloride, 15 mL of tetrahydrofuran and 1.62 mL (15.0 mmol) of 1,3-dimethyl-2-imidazolidinone were added to the residue to obtain Solution 2a.

[0197] In a sufficiently dried and argon-substituted 100 mL reactor, 2.17 g (15.0 mmol) of 4,7-dimethyl-1H-indene and 15 mL of tetrahydrofuran were charged, 10.2 mL of an n-butyllithium solution (hexane solution, 1.55 M, 15.8 mmol) was added, and the mixture was stirred at room temperature for 2 hours to obtain Solution 2b.

[0198] This Solution 2b was added dropwise to Solution 2a cooled to -78 °C, and stirring was continued for 15 hours while slowly returning to room temperature. An aqueous saturated ammonium chloride solution was added, the soluble components were extracted with hexane, the obtained fraction was washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography to obtain 2.06 g (yield 40%) of the target product represented by the following formula (A-2L) (hereinafter referred to as "Compound (A-2L)") as a mixture of isomers. 11H NMR (270 MHz, CDCl3) δ 7.24 (1H, s, Ar-H), 7.17 (1H, s, Ar-H), 7.00 - 6.93 (3H, m, Ar-H, C=CH-C), 6.87 - 6.84 (1H, d, C=CH-C), 6.63 - 6.61 (1H, dd, J = 5.4 Hz, J = 1.9 Hz, C=CH-C), 3.82 (1H, s, Si-CH), 3.27 (2H, s, Ar-CH2-C), 2.41 (3H, s, -CH3), 2.29 (6H, s, -CH3), 2.20 (3H, s, -CH3), 0.09 (3H, s, Si-CH3), 0.07 (3H, s, Si-CH3) ppm

[0199] [Chemical formula]

[0200] [Example 2A] 0.87 g (2.50 mmol) of the compound (A-2L) obtained in Synthesis Example 2-1, 20 mL of toluene, and 0.4 mL of tetrahydrofuran were charged into a sufficiently dried and argon-substituted 100 mL reactor and stirred. To this solution, 3.23 mL of an n-butyllithium solution (hexane solution, 1.55 M, 5.00 mmol) was added at room temperature, and then stirring was continued in an oil bath at 40 °C for 3 hours. The solution was cooled to 0 °C, 0.58 g (2.50 mmol) of zirconium tetrachloride was added, and stirring was continued at room temperature for 19 hours. After distilling off the solvent of the reaction solution, dichloromethane was added to the obtained solid to prepare a suspension, and the insoluble matter was removed with celite on a glass filter. After concentrating the obtained solution under reduced pressure, a suspension was prepared by adding n-hexane, the insoluble matter was filtered off with a glass filter, and the residue was dried under reduced pressure to obtain 0.84 g (yield 67%) of a yellow powdery compound (dimethylsilylene(5,6-dimethyl-2-indenyl)(4,7-dimethyl-1-indenyl)zirconium dichloride, hereinafter referred to as "transition metal compound (A-2)") represented by the following formula (A-2). 11H NMR (270 MHz, CDCl3) δ 7.31 (1H, s, Ar-H), 7.20 (1H, s, Ar-H), 7.07 - 7.06 (1H, d, J = 3.2 Hz, Ind-H), 7.00 - 6.98 (1H, d, J = 6.8 Hz, Ar-H), 6.89 - 6.87 (1H, d, J = 6.5 Hz, Ar-H), 6.37 - 6.36 (1H, d, J = 3.5 Hz, Ind-H), 5.98 - 5.97 (1H, d, J = 3.5 Hz, Ind-H), 2.57 (3H, s, -CH3), 2.36 (3H, s, -CH3), 2.31 (3H, s, -CH3), 2.26 (3H, s, -CH3), 1.06 (3H, s, Si-CH3), 0.91 (3H, s, Si-CH3) ppm FD - mass spectrometry (M + ): 502

[0201]

Chem.

[0202] [Comparative Example 1A] By the method of Synthesis Example 7 - 2 of JP - A - 2019 - 059933, a yellow powdery compound represented by the following formula (A - 3) (dimethylsilylene(2 - indenyl)(4,7 - dimethyl - 1 - indenyl)zirconium dichloride, hereinafter referred to as "transition metal compound (A - 3)") was synthesized.

[0203]

Chem.

[0204] [Example 1] <Preparation of Solid Catalyst Component (X - 1)>[[]] Using a reactor with a stirrer having an internal volume of 270 L, under a nitrogen atmosphere, as the solid support [S], silica gel (manufactured by Fuji Silysia Chemical Ltd., cumulative 50% particle size of volume distribution by laser light diffraction scattering method: 70 μm, specific surface area: 340 m 2 / g, pore volume: 1.3 cm 3 / g, dried at 250°C for 10 hours, hereinafter referred to as "solid support [S-1]".) 10 kg was suspended in 77 L of toluene and then cooled to 0 - 5°C. To this suspension, 19.4 liters of a toluene solution of methylaluminoxane (3.5 mol / L in terms of Al atoms) as component (B) was added dropwise over 30 minutes. At this time, the temperature inside the system was maintained at 0 - 5°C. Next, after contacting these at 0 - 5°C for 30 minutes, the temperature inside the system was raised to 95°C over 1.5 hours and then continuously contacted at 95°C for 4 hours. Thereafter, the temperature was lowered to room temperature, the supernatant was removed by decantation, and further washed twice with toluene to prepare a toluene slurry with a total volume of 115 L. When a part of the obtained slurry was sampled and analyzed, the solid content concentration was 122.6 g / L and the Al concentration was 0.612 mol / L.

[0205] Next, a 200 mL reactor equipped with a stirrer that had been sufficiently purged with nitrogen was charged with 30 mL of toluene and 1.63 mL (solid content weight: 0.2 g) of the above toluene slurry under a nitrogen atmosphere. Next, 5.0 μmol of the toluene solution of the transition metal compound (A-1) obtained in Example 1A was added as Zr, and these were contacted at a system temperature of 20 - 25°C for 1 hour. Then, the supernatant was removed by decantation and further washed twice with hexane. Thereby, a slurry of the solid catalyst component (X-1) with a total volume of 40 mL was prepared.

[0206] <Production of Ethylene-based Polymer> 500 milliliters of heptane was added to a 1 L SUS autoclave that had been sufficiently purged with nitrogen under a nitrogen atmosphere, and then ethylene was passed through to saturate the inside of the reactor with ethylene. Next, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and 30.0 mg of the above solid catalyst component (X-1) in slurry form as the solid content were charged. Then, the temperature was raised to 80°C and the pressure was raised to 0.8 MPaG with ethylene, and a polymerization reaction was carried out for 90 minutes. After filtering the obtained polymer, it was dried in vacuo at 80°C for 10 hours to obtain 160.2 g of an ethylene-based polymer. The catalyst activity was 5,340 g-PE / g-solid catalyst component.

[0207] [Example 2] <Preparation of Solid Catalyst Component (X-2)> A slurry of the solid catalyst component (X-2) was prepared in the same manner as in Example 1, except that the transition metal compound (A-2) obtained in Example 2A was used instead of the transition metal compound (A-1).

[0208] <Production of Ethylene Polymer> The same operations as in <Production of Ethylene Polymer> of Example 1 were carried out, except that 20.0 mg of the solid catalyst component (X-2) in slurry form was charged as the solid content instead of the solid catalyst component (X-1), and 80.1 g of an ethylene polymer was obtained. The catalytic activity was 8,010 g-PE / g-solid catalyst component. The results are shown in Table 8.

[0209] [Comparative Example 1] <Preparation of Solid Catalyst Component (X-3)> A slurry of the solid catalyst component (X-3) was prepared in the same manner as in Example 1, except that the compound (A-3) obtained in Comparative Example 1A was used instead of the compound (A-1).

[0210] <Production of Ethylene Polymer> The same operations as in <Production of Ethylene Polymer> of Example 1 were carried out, except that 250 mg of the solid catalyst component (X-3) in slurry form was charged as the solid content instead of the solid catalyst component (X-1), and 80.0 g of an ethylene polymer was obtained. The catalytic activity was 2,670 g-PE / g-solid catalyst component. The results are shown in Table 8.

[0211]

Table 8

[0212] In Examples 1 and 2 using the transition metal compound [A] of the present invention (a bridged (2-indenyl)(1-indenyl) type compound having a substituent at a specific position of the 2-indenyl ring), higher catalytic activity was shown compared to Comparative Example 1 using a bridged (2-indenyl)(1-indenyl) type compound having no such substituent.

[0213] In Examples 1 and 2, the MFR of the resulting ethylene-based polymer increased as compared with Comparative Example 1. In Examples 1 and 2, the terminal vinyl ratio of the resulting ethylene-based polymer increased as compared with Comparative Example 1.

[0214] [Example 3] [Production of Ethylene-Based Polymer] 500 milliliters of toluene was added to a 1-liter SUS autoclave with sufficient nitrogen substitution under a nitrogen atmosphere. Next, 0.4 mmol of methylaluminoxane was charged, and then 0.2 μmol of a toluene solution of compound (A-1) was added. This solution was pressurized with 0.6 MPaG of ethylene and 0.12 MPaG of propylene, heated to 85°C, and subjected to a polymerization reaction for 5 minutes. The polymerization reaction solution was deashed with hydrochloric acid and methanol, and the obtained polymer was filtered and then vacuum dried at 80°C for 10 hours to obtain 7.6 g of an ethylene-based polymer. The catalytic activity was 73,870 g-PE / g-catalyst component. The results are shown in Table 9.

[0215] [Table 9]

[0216] Even in solution polymerization, the terminal vinyl ratio of the resulting ethylene-based polymer is very high.

Claims

1. A transition metal compound [A] represented by the following general formula [1]. 【Chemical 1】 (In general formula [1], M is a Group 4 transition metal atom in 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, or a hydrocarbon 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 is a Group 14 atom in the periodic table, R 1 、 R 2 、 R 5 、 R 6 、 R8、 R 10 、 R 11 、 R 13 and R 14 are hydrogen atoms, R 3 and R 4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms, or a sulfur-containing group having 1 to 20 carbon atoms, and may be bonded to each other to form a ring which may have a substituent. R 7 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, or an aromatic heterocyclic five-membered ring substituent that may have a hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from nitrogen, oxygen, and sulfur in the heterocyclic ring, R 9 and R 12 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms, or a sulfur-containing group having 1 to 20 carbon atoms (provided that R 9 is not a substituent represented by the following general formula [1-1], and R9 is not a naphthyl group, an anthracenyl group, a phenanthryl group, a julolidinyl group, a furyl group, a thienyl group, a benzothienyl group, a pyrrolidinyl group, a pyrrolyl group, an indolyl group, or a carbazolyl group). 【Chemical Formula 1-1】 (In general formula [1-1], R 9a , R 9b , R 9c , R 9d and R 9e are each independently a hydrogen atom, a hydrocarbon group, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group, * represents a bond to the indenyl ring. )), R 1 ~R 6 Among adjacent substituents of R 1 ~R 6 , they may be bonded to each other to form a ring which may have a substituent. R 7 to R 12 Among them, adjacent substituents may combine with each other to form a ring which may have a substituent.

2. In the general formula [1], M is a zirconium atom or a hafnium atom, X is independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, Q is a carbon atom or a silicon atom The transition metal compound [A] according to claim 1.

3. In the general formula [1], Q is a silicon atom, R3 and R 4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms, and may be bonded to each other to form a ring which may have a substituent, R 7 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing group having 1 to 20 carbon atoms, R 9 and R 12 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, or a nitrogen-containing group having 1 to 20 carbon atoms The transition metal compound [A] according to claim 2.

4. The transition metal compound [A] according to claim 3, wherein R 7 is a hydrogen atom in the general formula [1].

5. In the general formula [1], R 3 and R 4 The transition metal compound [A] according to claim 4, wherein at least one of them is a hydrocarbon group having 1 to 20 carbon atoms.

6. In the general formula [1], R 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, and may be bonded to each other to form a ring which may have a substituent. The transition metal compound [A] according to claim 5.

7. In the general formula [1], R 9 The transition metal compound [A] according to claim 5 or 6, wherein R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

8. In the general formula [1], R 12 The transition metal compound [A] according to claim 7, wherein R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

9. A catalyst for olefin polymerization containing the transition metal compound [A] according to any one of claims 1 to 8.

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

11. A method for producing an olefin polymer, including a step of polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 9 or 10.

12. The method for producing an olefin polymer according to claim 11, wherein the step of polymerizing the olefin is a step of homopolymerizing ethylene or a step of copolymerizing ethylene and an α-olefin having 3 or more and 20 or less carbon atoms.

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