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

Abstract

To provide a transition metal compound excellent in olefin polymerization activity, an olefin polymerization catalyst containing the transition metal compound, and a method for producing an olefin polymer in the presence of the catalyst.SOLUTION: For example, it is a compound (A) represented by the following formula.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Titanium-based catalysts consisting of titanium compounds and organoaluminum compounds, and vanadium-based catalysts consisting of vanadium compounds and organoaluminum compounds are known as catalysts for producing olefin polymers such as ethylene polymers and ethylene-α-olefin copolymers.

[0003] Furthermore, metallocene catalysts comprising a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane) are known as catalysts capable of producing olefin polymers with high polymerization activity.

[0004] In recent years, various postmetallocene catalysts have been reported as next-generation olefin polymerization catalysts (e.g., Non-Patent Document 1). In the technical field of olefin polymerization catalysts, it is extremely important to research and provide highly active and highly functional postmetallocene catalysts. Among them, postmetallocene catalysts with multidentate ligands are attractive in terms of their stability and functionality, but few highly active catalysts that can be used industrially are known, and their development is strongly desired.

[0005] On the other hand, the present applicant has already found that by converting the ligand skeleton and substituents, it is possible to highly activate olefin polymerization catalysts and to impart various functions and features to the resulting olefin polymers (e.g., Non-Patent Document 2).

[0006] Patent Document 1 discloses a transition metal compound that exhibits high olefin polymerization activity and can be used to synthesize a wide range of polymers from low molecular weight oligomers to high molecular weight polymers. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-193612 [Non-patent literature]

[0008] [Non-Patent Document 1] Chemical Reviews 2003, 103, 283-315. [Non-patent document 2] Chemical Reviews 2011, 111, 2363-2449. Summary of the Invention [Problem to be solved by the invention]

[0009] Patent Document 1 discloses a transition metal compound that exhibits high olefin polymerization activity, but there has been a demand for a transition metal compound that has even higher polymerization activity. Therefore, an object of the present invention is to provide a transition metal compound having excellent olefin polymerization activity, an olefin polymerization catalyst containing the transition metal compound, and a process for producing an olefin polymer in the presence of the catalyst. [Means for solving the problem]

[0010] The present invention relates to, for example, the following [1] to

[11] . [1] A transition metal compound [A] represented by the following general formula (I): [ka] (In the general formula (I), R 1 ~R 9 and R 12 ~R 14each independently represents a hydrogen atom, a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen atom, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group; R 1 ~R 9 and R 12 ~R 14 Adjacent substituents among the above may be bonded to each other to form a ring, R 10 and R 11 each independently represents a fused polycyclic hydrocarbon group or a fused heterocyclic compound group, and the fused polycyclic hydrocarbon group and the fused heterocyclic compound group may further have a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen atom, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group as a substituent; D 1 and D 2 are each independently -OR 15 , -SR 15 , -NR 16 R 17 , or -PR 16 R 17 (The solid lines indicate bonds with adjacent atoms. R 15 is a hydrocarbon group having two or more carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group, and R 16 and R 17 are each independently a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group; L 1 and L 2 are each independently an oxygen atom, a sulfur atom, [ka] (The solid lines indicate bonds with adjacent atoms. R 18is a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen atom, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group; M is a transition metal atom of Group 4 of the periodic table, Two Xs each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen-containing hydrocarbon group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a germanium-containing group, a tin-containing group, or a diene-based divalent derivative group, and two Xs may be bonded to each other to form a ring.

[0011] [2] R 10 and R 11 are each independently a fused polycyclic hydrocarbon group or a fused heterocyclic compound group which may have a hydrocarbon group as a substituent.

[0012] [3] The above D 1 and D 2 are each independently, -OR 15 and R 15 is a residue of a hydrocarbon group having 2 to 20 carbon atoms other than an aryl group, an aryl group having 7 to 25 carbon atoms, a silicon-containing group, a halogen-containing hydrocarbon group, or a heterocyclic compound containing an oxygen atom, a sulfur atom, or a nitrogen atom.

[0013] [4] R 15 The transition metal compound [A] according to [3], wherein is a linear or branched alkyl group having 3 to 15 carbon atoms or a cyclic saturated hydrocarbon group having 3 to 15 carbon atoms.

[0014] [5] Said L 1 and L 2 The transition metal compound [A] according to any one of [1] to [4], wherein is an oxygen atom.

[0015] [6] The transition metal compound [A] according to any one of [1] to [5], wherein M is a zirconium atom or a hafnium atom.

[0016] [7] An olefin polymerization catalyst comprising the transition metal compound [A] according to any one of [1] to [6].

[0017] [8] Organometallic compounds [B-1], and The olefin polymerization catalyst according to [7], further comprising at least one compound [B] selected from the group consisting of compounds [B-2] that react with the transition metal compound [A] to form an ion pair.

[0018] [9] The olefin polymerization catalyst according to [7] or [8], further comprising a support, wherein the transition metal compound [A] is supported on the support.

[0019]

[10] A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of [7] to [9].

[0020]

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

[10] , wherein the olefin is at least one selected from the group consisting of α-olefins having 2 to 30 carbon atoms, cyclic olefins, and non-conjugated diolefins. [Effects of the Invention]

[0021] According to the transition metal compound, olefin polymerization catalyst, and process for producing an olefin polymer of the present invention, olefins can be polymerized with excellent polymerization activity. DETAILED DESCRIPTION OF THE INVENTION

[0022] In the present invention, the term "polymerization" is used to encompass both "homopolymerization" and "copolymerization." Furthermore, the term "polymer" is used to encompass both "homopolymer" and "copolymer." In the present invention, the term "hydrocarbon group" refers to a substituent group consisting of only carbon atoms and hydrogen atoms. In the present invention, the term "olefin" refers to a hydrocarbon having one or more carbon-carbon double bonds in the molecule. In the present invention, a numerical range described using "to" means that the numerical values ​​before and after "to" are included as the lower limit and upper limit. In the present invention, when the units of the values ​​written before and after "~" indicating a numerical range are the same, the unit of the values ​​written before "~" may be omitted. For example, "45°C to 90°C" may be written as "45 to 90°C." In the present invention, "room temperature" means 23°C.

[0023] <Transition metal compound [A]> The transition metal compound [A] according to the present invention is represented by the following general formula (I).

[0024] [ka] In the general formula (I), R 1 ~R 9 and R 12 ~R 14 are each independently a hydrogen atom, a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen atom, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group.

[0025] Examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an n-hexyl group, an n-octyl group, a nonyl group, a dodecyl group, and an eicosyl group; linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as a vinyl group, a propenyl group, a but-3-en-1-yl group, a crotyl group, a pent-4-en-1-yl group, a pent-3-en-1-yl group, a pent-2-en-1-yl group, an isopentenyl group, a 2-methylbut-3-en-1-yl group, a pent-4-en-2-yl group, an allyl group, and an isopropenyl group; linear or branched alkynyl groups having 2 to 30, preferably 2 to 20, carbon atoms, such as an ethynyl group and a propargyl group; cyclic saturated hydrocarbon groups having 3 to 30, preferably 3 to 20, carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 1-methylcyclopentyl group, a cyclohexyl group, a 1-methylcyclohexyl group, a norbornyl group, and an adamantyl group; cyclic unsaturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, other than aryl groups, such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, and a cyclopentadienyl group; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, an acenaphthyl group, a phenalenyl group, an aceanthrylenyl group, a tetrahydronaphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, a pyrenyl group, an adanyl group, an indenyl group, a fluorenyl group, and an anthracenyl group; alkyl-substituted aryl groups having 7 to 30 carbon atoms, preferably 7 to 20 carbon atoms, such as a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a methylnaphthyl group, an isopropylphenyl group, a tert-butylphenyl group, a dimethylphenyl group, a di-tert-butylphenyl group, and a tri-isopropylphenyl group; Examples of aryl-substituted alkyl groups include those having 7 to 30, preferably 7 to 20, carbon atoms, such as benzyl, cumyl, 2-methylbenzyl, 4-methylbenzyl, 2,4,6-trimethylbenzyl, 3,5-dimethylbenzyl, cuminyl, 2,4,6-triisopropylbenzyl, 4-tert-butylbenzyl, 3,5-di-tert-butylbenzyl, 1-phenylethyl, and trityl groups.

[0026] Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. Examples of hydrocarbon-substituted silyl groups include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-tert-butylsilyl, dimethyl(pentafluorophenyl)silyl, and tribenzylsilyl groups. Examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group, a triethylsiloxy group, a triphenylsiloxy group, and a tribenzylsiloxy group.

[0027] The silicon-containing group preferably has 0 to 30 carbon atoms, and more preferably 0 to 20 carbon atoms.

[0028] Examples of the oxygen-containing group include a hydroxyl group, an alkoxy group, an aryloxy group, an arylalkoxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a peroxy group, a carboxylic anhydride group, and a residue of a heterocyclic compound containing an oxygen atom. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy groups. Examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, a 2,4,6-trimethylphenoxy group, and a 3,5-di-tert-butylphenoxy group.

[0029] Arylalkoxy groups include, for example, phenylmethoxy and phenylethoxy groups. Examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group. Examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group.

[0030] Examples of residues of heterocyclic compounds containing an oxygen atom include a furyl group, a pyranyl group, a benzofuranyl group, an isobenzofuranyl group, a chromenyl group, a xanthenyl group, a phenoxathiinyl group, an isoxazolyl group, an isochromanyl group, a chromanyl group, a furazanyl group, and a morpholinyl group.

[0031] The oxygen-containing group preferably has 0 to 30 carbon atoms, and more preferably 0 to 20 carbon atoms. The residue of the heterocyclic compound containing an oxygen atom may have the hydrocarbon group as a substituent.

[0032] Examples of the sulfur-containing group include a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, an isocyanate ester group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, a sulfenyl group, and a residue of a heterocyclic compound containing a sulfur atom. Examples of thioester groups include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl groups. Examples of the alkylthio group include a methylthio group and an ethylthio group.

[0033] Examples of the arylthio group include a phenylthio group, a methylphenylthio group, and a naphthylthio group. Examples of sulfonate groups include methyl sulfonate groups, ethyl sulfonate groups, and phenyl sulfonate groups. Examples of the sulfonamide group include a phenylsulfonamide group, an N-methylsulfonamide group, and an N-methyl-p-toluenesulfonamide group. Examples of residues of heterocyclic compounds containing a sulfur atom include a thienyl group, a benzo[b]thienyl group, a naphtho[2,3-b]thienyl group, a thianthrenyl group, a thiophenyl group, and a benzothiophenyl group.

[0034] The sulfur-containing group preferably has 0 to 30 carbon atoms, and more preferably 0 to 20 carbon atoms. The residue of the heterocyclic compound containing a sulfur atom may have the above-mentioned hydrocarbon group as a substituent.

[0035] Examples of the nitrogen-containing group include an amino group, an imino group, an amido group, an imido group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, an amino group in the form of an ammonium salt, and a residue of a heterocyclic compound containing a nitrogen atom. Examples of the amino group include alkylamino groups and arylamino groups such as dimethylamino, ethylmethylamino, and diphenylamino groups.

[0036] Examples of the imino group include alkylimino and arylimino groups such as methylimino, ethylimino, propylimino, butylimino, and phenylimino groups. Examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group. Examples of the imide group include an acetimide group and a benzimide group.

[0037] Examples of the residue of a heterocyclic compound containing a nitrogen atom include a 2H-pyrrolyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an indolizinyl group, an isoindolyl group, a 3H-indolyl group, an indolyl group, a 1H-indazolyl group, a purinyl group, a 4H-quinolidinyl group, an isoquinolyl group, a quinolyl group, a phthalazinyl group, a naphthyridinyl group, a quinoxanilyl group, a quinazolinyl group, a cinnolinyl group, a pteridinyl group, a 4aH-carbazol-4a-yl group, an N-carbazolyl group, and a 9H-carbazol-1-yl group. , 9H-carbazol-2-yl group, 9H-carbazol-3-yl group, 9H-carbazol-4-yl group, phenanthridinyl group, acridinyl group, phenanthrolinyl group, phenazinyl group, phenarsazinyl group, isothiazolyl group, perimidinyl group, phenothiazinyl group, phenoxazinyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, triazinyl group, and phenanthrolinyl group. N-carbazolyl group may or may not be hydrogenated.

[0038] The nitrogen-containing group preferably has 0 to 30 carbon atoms, and more preferably 0 to 20 carbon atoms. The residue of the heterocyclic compound containing a nitrogen atom may have the above-mentioned hydrocarbon group as a substituent.

[0039] The halogen atoms include fluorine, chlorine, bromine, and iodine.

[0040] The halogen-containing hydrocarbon group is a hydrocarbon group in which a hydrogen atom is substituted with a halogen atom. Examples of the halogen-containing hydrocarbon group include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group.

[0041] Examples of the boron-containing group include a boranediyl group, a boranetriyl group, and a diboranyl group. Examples of the phosphorus-containing group include a phosphido group, a phosphoryl group, a thiophosphoryl group, and a phosphato group. Examples of the germanium-containing group and the tin-containing group include groups in which the silicon of the silicon-containing group is substituted with germanium or tin.

[0042] R 1 ~R 9 and R 12 ~R 14 is preferably a hydrogen atom, a hydrocarbon group, a halogen atom, a halogen-containing hydrocarbon group, or a residue of a heterocyclic compound containing an oxygen atom, a sulfur atom, or a nitrogen atom, and more preferably a hydrogen atom or a hydrocarbon group. Among them, the above-mentioned R 2 and R 5 From the viewpoint of ease of obtaining raw materials and ease of synthesis of the transition metal compound [A], is preferably a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen atom, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group, more preferably a hydrocarbon group, a halogen atom, a halogen-containing hydrocarbon group, or a residue of a heterocyclic compound containing an oxygen atom, a sulfur atom, or a nitrogen atom, and even more preferably a hydrocarbon group. Also, R 8 and R 13 From the same viewpoint as above, is preferably a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen atom, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group, more preferably a hydrocarbon group, a halogen atom, a halogen-containing hydrocarbon group, or a residue of a heterocyclic compound containing an oxygen atom, a sulfur atom, or a nitrogen atom, and even more preferably a hydrocarbon group.

[0043] From the viewpoints of ease of raw material availability and ease of synthesis of the transition metal compound [A], the hydrocarbon group is preferably a linear or branched alkyl group having 1 to 30 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 30 carbon atoms, a cyclic unsaturated hydrocarbon group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkyl-substituted aryl group having 7 to 30 carbon atoms, or an aryl-substituted alkyl group having 7 to 30 carbon atoms, more preferably a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, an cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, still more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and particularly preferably a linear or branched alkyl group having 1 to 5 carbon atoms.

[0044] R 1 ~R 9 and R 12 ~R 14 Adjacent substituents among these may be bonded to each other to form a ring, or may not be bonded to each other. Examples of the ring include an aliphatic ring, an aromatic ring, and a heterocycle containing a heteroatom. The ring may further have a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen atom, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group. Examples of the hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, halogen atom, halogen-containing hydrocarbon group, boron-containing group, phosphorus-containing group, germanium-containing group, and tin-containing group that the ring may have include, for example, the R 1 ~R 9 and R 12 ~R 14 Examples of the halogen atom include the same groups as the hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, halogen atoms, halogen-containing hydrocarbon groups, boron-containing groups, phosphorus-containing groups, germanium-containing groups, and tin-containing groups exemplified above.

[0045] In the general formula (I), R 10 and R 11are each independently a condensed polycyclic hydrocarbon group or a condensed heterocyclic compound group. Examples of condensed polycyclic hydrocarbon groups include pentalenyl, indenyl, naphthyl, azulenyl, and heptalenyl groups; biphenylenyl, as-indacenyl, and s-indacenyl groups, acenaphthylenyl, fluorenyl, phenalenyl, phenanthryl, and anthracenyl groups; fluoranthenyl, acephenanthrylenyl, and aceanthrylenyl groups, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, and pleiadenyl groups; picenyl, perylenyl, pentaphenyl, pentacenyl, and tetraphenylenyl groups.

[0046] Examples of the fused heterocyclic compound group include an indolinyl group, an isoindolinyl group, a 2-methylindolinyl group, a 2,3-dimethylindolinyl group, an indolyl group, a 3H-indolyl group, an isoindolyl group, a 2-phenylindolyl group, a 4,5,6,7-tetrahydroindolyl group, a perhydroindolyl group, a perhydroisoindolyl group, a 4aH-carbazol-4a-yl group, an N-carbazolyl group, a 9H-carbazol-1-yl group, a 9H-carbazol-2-yl group, a 9H-carbazol-3-yl group, a 9H-carbazol-4-yl group, a 3,6-di-tert-butyl-9H-carbazol-9-yl group, and 1,2,3,4-tetrahydro-9H-carbazole. N-carbazolyl groups include 1H-indazolyl, purinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxanyl, quinazolinyl, cinnolinyl, pteridinyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl, isochromanyl, and chromanyl. N-carbazolyl groups may be hydrogenated or unhydrogenated.

[0047] The condensed polycyclic hydrocarbon group and the condensed heterocyclic compound group may further have a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen atom, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group as a substituent. Examples of the hydrocarbon group, the silicon-containing group, the oxygen-containing group, the sulfur-containing group, the nitrogen-containing group, the halogen atom, the halogen-containing hydrocarbon group, the boron-containing group, the phosphorus-containing group, the germanium-containing group, and the tin-containing group that the condensed polycyclic hydrocarbon group and the condensed heterocyclic compound group may have include, for example, the R 1 ~R 9 and R 12 ~R 14 Examples of the halogen atom include the same groups as the hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, halogen atoms, halogen-containing hydrocarbon groups, boron-containing groups, phosphorus-containing groups, germanium-containing groups, and tin-containing groups exemplified above.

[0048] In the transition metal compound [A], the R 10 and R 11 is a condensed polycyclic hydrocarbon group or a condensed heterocyclic compound group, and R 10 and R 11 When is a bulky group, the olefin polymerization activity of the transition metal compound [A] is improved. The condensed polycyclic hydrocarbon group and the condensed heterocyclic compound group are R 10 and R 11 When the transition metal compound [A] is bonded to the benzene ring so as to extend in a direction perpendicular to the bonding direction between the transition metal compound [A] and the benzene ring, deactivation of the transition metal compound [A] is suppressed even when an organometallic compound such as an organoaluminum compound described later is used as a co-catalyst, and the transition metal compound [A] has high olefin polymerization activity. The condensed polycyclic hydrocarbon group and the condensed heterocyclic compound group are R 10 and R 11 Even when the transition metal compound [A] is bonded to the benzene ring so as to extend in a direction parallel to the bond direction between the transition metal compound [A] and the benzene ring, it is presumed that the transition metal compound [A] has high olefin polymerization activity because the counter anion can be physically kept farther away when a bulky cocatalyst is used.

[0049] R 10 and R 11 From the viewpoint of polymerization activity, is preferably a fused polycyclic hydrocarbon group or a fused heterocyclic compound group which may have a hydrocarbon group, more preferably a fused heterocyclic compound group which may have a hydrocarbon group having 1 to 30 carbon atoms, even more preferably a fused heterocyclic compound group which may have a linear or branched alkyl group having 1 to 20 carbon atoms, still more preferably a fused tricyclic fused heterocyclic compound group which may have a linear or branched alkyl group having 1 to 10 carbon atoms, and particularly preferably an N-carbazolyl group which may have a linear or branched alkyl group having 1 to 5 carbon atoms.

[0050] In the general formula (I), D 1 and D 2 are each independently -OR 15 , -SR 15 , -NR 16 R 17 , or -PR 16 R 17 A solid line indicates a bond between adjacent atoms, for example, a covalent bond between adjacent atoms.

[0051] R 15 is a hydrocarbon group having two or more carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group. R 16 and R 17 are each independently a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group. Examples of the hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, halogen-containing hydrocarbon group, boron-containing group, phosphorus-containing group, germanium-containing group, and tin-containing group include the R 1 ~R 9 and R 12 ~R 14Examples of the hydrocarbon group include the same groups as the hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, halogen-containing hydrocarbon group, boron-containing group, phosphorus-containing group, germanium-containing group, and tin-containing group exemplified above.

[0052] The above D 1 and D 2 is preferably -OR from the viewpoint of polymerization activity. 15 or -NR 16 R 17 and more preferably -OR 15 is.

[0053] R 15 From the viewpoint of polymerization activity, is preferably a hydrocarbon group having 2 or more carbon atoms, a silicon-containing group, a halogen-containing hydrocarbon group, or a residue of a heterocyclic compound containing an oxygen atom, a sulfur atom, or a nitrogen atom, more preferably a hydrocarbon group having 2 to 20 carbon atoms other than an aryl group, an aryl group having 7 to 25 carbon atoms, a silicon-containing group, a halogen-containing hydrocarbon group, or a residue of a heterocyclic compound containing an oxygen atom, a sulfur atom, or a nitrogen atom, and even more preferably a hydrocarbon group having 2 to 20 carbon atoms other than an aryl group or an aryl group having 7 to 25 carbon atoms.

[0054] R 15 When R is a phenyl group, 15 has only two-dimensional extent, but R 15 is a hydrocarbon group having 2 to 20 carbon atoms other than an aryl group or an aryl group having 7 to 25 carbon atoms, particularly a group having three-dimensional extent, D 1 and D 2 In addition to being bulky, R 15 It is presumed that the transition metal compound [A] has a higher olefin polymerization activity because R can more effectively block the space where deactivating compounds can approach. 15is preferably a hydrocarbon group other than an aryl group having 3 to 20 carbon atoms or an aryl group having 7 to 25 carbon atoms, more preferably a hydrocarbon group other than an aryl group having 3 to 15 carbon atoms or an aryl group having 7 to 20 carbon atoms, even more preferably a hydrocarbon group other than an aryl group having 3 to 15 carbon atoms or an aryl group having 7 to 15 carbon atoms, and particularly preferably a hydrocarbon group other than an aryl group having 3 to 15 carbon atoms.

[0055] R 15 When R is a hydrocarbon group having 3 to 15 carbon atoms other than an aryl group, 15 R is preferably a linear or branched alkyl group having 3 to 15 carbon atoms or a cyclic saturated hydrocarbon group having 3 to 15 carbon atoms. 15 is a linear or branched alkyl group having 3 to 15 carbon atoms or a cyclic saturated hydrocarbon group having 3 to 15 carbon atoms, R 15 In addition to being able to more effectively block the space that deactivating compounds can access, R 15 Since R does not have an unsaturated bond, the coordinate bond in the metal cation is less likely to be inhibited, and therefore, it is presumed that the transition metal compound [A] has a higher olefin polymerization activity. 15 is preferably a linear or branched alkyl group having 3 to 10 carbon atoms or a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 3 to 5 carbon atoms (for example, an isopropyl group).

[0056] R 16 and R 17 From the viewpoint of polymerization activity, is preferably a hydrocarbon group, a silicon-containing group, a halogen-containing hydrocarbon group, or a residue of a heterocyclic compound containing an oxygen atom, a sulfur atom, or a nitrogen atom, more preferably a hydrocarbon group, even more preferably a hydrocarbon group having 2 or more carbon atoms, still more preferably a hydrocarbon group having 2 to 30 carbon atoms, and particularly preferably a linear or branched alkyl group having 3 to 10 carbon atoms or a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms.

[0057] In the transition metal compound [A],1 and D 2 -OR 15 or -SR 15 and R 15 is a bulky hydrocarbon group, particularly a hydrocarbon group having two or more carbon atoms, 10 and R 11 is a bulky fused polycyclic hydrocarbon group or a fused heterocyclic compound group having a large planar extent, deactivation of the transition metal compound [A] is suppressed even when an organometallic compound such as an organoaluminum compound described later is used as a co-catalyst, and the transition metal compound [A] has high olefin polymerization activity. The above D 1 and D 2 Ga-NR 16 R 17 or -PR 16 R 17 If R 16 and R 17 For example, even if the group is a methyl group, D 1 and D 2 has two methyl groups, it is presumed that, for the same reason as above, deactivation of the transition metal compound [A] is suppressed and polymerization activity is improved.

[0058] The above D 1 and D 2 are preferably the same as each other from the viewpoint of ease of synthesis of the transition metal compound [A]. From the viewpoint of ease of synthesis of the transition metal compound [A], 1 and D 2 -OR 15 If D 1 R in 15 And, D 2 R in 15 are preferably the same substituents, and D 1 and D 2 Ga-SR 15 If D 1 R in 15 And, D 2 R in 15 and are preferably the same substituents. 1 R in 15and D 2 R in 15 and are the same substituents, D 1 R in 15 and D 2 R in 15 This means that the specific substituent represented by D is the same as the substituent represented by D. 1 R in 15 and D 2 R in 15 and are the same substituents, for example, D 1 R in 15 and D 2 R in 15 and are both isopropyl groups. From the viewpoint of ease of synthesis of the transition metal compound [A], 1 and D 2 Ga-NR 16 R 17 If D 1 R in 16 And, D 2 R in 16 are preferably the same substituents, and D 1 R in 17 And, D 2 R in 17 and are preferably the same substituents. 1 and D 2 Ga-PR 16 R 17 If D 1 R in 16 And, D 2 R in 16 are preferably the same substituents, and D 1 R in 17 And, D 2 R in 17 and are preferably the same substituents.

[0059] Among the transition metal compounds and olefin polymerization catalysts described in Patent Document 1, the transition metal compound [A] has particularly excellent olefin polymerization activity.

[0060] In the general formula (I), L 1 and L 2 are each independently an oxygen atom, a sulfur atom, [ka] Solid lines indicate bonds to adjacent atoms.

[0061] R 18 is a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen atom, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group. Examples of the hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, halogen atom, halogen-containing hydrocarbon group, boron-containing group, phosphorus-containing group, germanium-containing group, and tin-containing group include, for example, the R 1 ~R 9 and R 12 ~R 14 Examples of the halogen atom include hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, halogen atoms, halogen-containing hydrocarbon groups, boron-containing groups, phosphorus-containing groups, germanium-containing groups, and tin-containing groups.

[0062] Said L 1 and L 2 is preferably an oxygen atom.

[0063] In the general formula (I), M is a transition metal atom of Group 4 of the periodic table. Examples of M include a titanium atom, a zirconium atom, and a hafnium atom. From the viewpoint of polymerization activity, the M is preferably a zirconium atom or a hafnium atom. The transition metal compound [A] in which M is a hafnium atom has a greater effect of increasing polymerization activity than the transition metal compound [A] in which M is a zirconium atom.

[0064] In general formula (I), D 1 and M, and D 2 The bond between L and M is a coordinate bond, 1and M, and L 2 The bond between and M is a covalent bond. For example, D 1 -OR 15 In the case where the oxygen atom and the carbon atom of the benzene ring are bonded by a covalent bond, the oxygen atom and M are bonded by a coordinate bond.

[0065] In the general formula (I), each of the two Xs is independently a hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen-containing hydrocarbon group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a germanium-containing group, a tin-containing group, or a divalent diene derivative group. The two Xs may be bonded to each other to form a ring, or may not be bonded to each other. X forms a covalent bond, a coordinate bond, or an ionic bond with M.

[0066] The halogen atoms include fluorine, chlorine, bromine, and iodine. The hydrocarbon group may be R 1 ~R 9 and R 12 ~R 14 Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl; alkenyl groups such as vinyl, propenyl, and cyclohexenyl; aryl groups such as phenyl, naphthyl, and anthracenyl; alkyl-substituted aryl groups such as tolyl, dimethylphenyl, and tri-isopropylphenyl; and aryl-substituted alkyl groups such as benzyl, cumyl, and trityl. Examples of the halogen-containing hydrocarbon group include groups in which at least one hydrogen atom in the hydrocarbon group having 1 to 20 carbon atoms has been substituted with a halogen atom.

[0067] The silicon-containing group includes R1 ~R 9 and R 12 ~R 14 Specific examples include hydrocarbon-substituted silyl groups such as phenylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, tritolylsilyl group, and trinaphthylsilyl group; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether group; silicon-substituted alkyl groups such as trimethylsilylmethyl group; and silicon-substituted aryl groups such as trimethylsilylphenyl group.

[0068] The oxygen-containing group is R 1 ~R 9 and R 12 ~R 14 Specific examples include a hydroxy group; alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; aryloxy groups such as a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, and a naphthoxy group; arylalkoxy groups such as a phenylmethoxy group and a phenylethoxy group; an acetoxy group; a carbonyl group; and residues of heterocyclic compounds containing an oxygen atom.

[0069] The sulfur-containing group is R 1 ~R 9 and R 12 ~R 14Specific examples include sulfonate groups such as a methyl sulfonate group, a trifluoromethanesulfonate group, a phenyl sulfonate group, a benzyl sulfonate group, a p-toluenesulfonate group, a trimethylbenzenesulfonate group, a triisobutylbenzenesulfonate group, a p-chlorobenzenesulfonate group, and a pentafluorobenzenesulfonate group; sulfinate groups such as a methyl sulfinate group, a phenyl sulfinate group, a benzyl sulfinate group, a p-toluenesulfinate group, a trimethylbenzenesulfinate group, and a pentafluorobenzenesulfinate group; an alkylthio group; an arylthio group; and a residue of a heterocyclic compound containing a sulfur atom.

[0070] The nitrogen-containing group is R 1 ~R 9 and R 12 ~R 14 Specific examples include an amino group; alkylamino groups such as a methylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, and a dicyclohexylamino group; arylamino groups or alkylarylamino groups such as a phenylamino group, a diphenylamino group, a ditolylamino group, a dinaphthylamino group, and a methylphenylamino group; and residues of heterocyclic compounds containing a nitrogen atom.

[0071] Examples of the boron-containing group include BR4 (R is a hydrogen atom, an alkyl group, an aryl group which may have a substituent, or a halogen atom).

[0072] Examples of the aluminum-containing group include AlR4 (R is a hydrogen atom, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.).

[0073] Examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine group, tributylphosphine group, and tricyclohexylphosphine group; triarylphosphine groups such as triphenylphosphine group and tritolylphosphine group; phosphite groups (phosphido groups) such as methylphosphine group, ethylphosphite group, and phenylphosphite group; phosphonic acid groups; and phosphinic acid groups.

[0074] Examples of the germanium-containing group include R 1 ~R 9 and R 12 ~R 14 Examples of the silicon-containing group include groups in which the silicon atom in the silicon-containing group exemplified above is substituted with germanium.

[0075] Examples of the tin-containing group include R 1 ~R 9 and R 12 ~R 14 Examples of the silicon-containing group include groups in which the silicon atom in the silicon-containing group exemplified above is substituted with tin.

[0076] Examples of the diene-based divalent derivative group include a 1,3-butadienyl group, an isoprenyl (2-methyl-1,3-butadienyl) group, a piperylenyl (1,3-pentadienyl) group, a 2,4-hexadienyl group, a 1,4-diphenyl-1,3-pentadienyl group, and a metallocyclopentene group such as a cyclopentadienyl group.

[0077] The X is preferably a halogen atom or a hydrocarbon group, and more preferably a hydrocarbon group having 1 to 30 carbon atoms.

[0078] <Method of producing the transition metal compound [A]> The transition metal compound [A] can be produced, for example, by the following method.

[0079] <Production of the ligand constituting the transition metal compound [A]> The ligand constituting the transition metal compound [A] can be obtained, for example, by the Suzuki-Miyaura coupling reaction of a 3,3'-dibromo-2,2'-dialkoxybiaryl with a boronic acid derived from a phenol, or by the Suzuki-Miyaura coupling reaction of a boronic acid derived from a 2,2'-dialkoxybiaryl with a halogenated phenol, followed by removal of the protecting group, if any, with an appropriate deprotecting agent. Furthermore, a new ligand can be obtained by further converting the alkoxy group of the obtained ligand. The protecting group may also be removed with a deprotecting agent prior to the Suzuki-Miyaura coupling reaction.

[0080] Suzuki-Miyaura Coupling Reaction of 3,3'-Dibromo-2,2'-dialkoxybiaryls with Boronic Acids Derived from Phenols Specifically, the Suzuki-Miyaura coupling reaction of 3,3'-dibromo-2,2'-dialkoxybiaryls with boronic acids derived from phenols is carried out by adding solvent 1 to a mixture of these compounds, a basic compound, a palladium catalyst, and a compound that acts as a ligand for the palladium catalyst. These may or may not be dissolved in solvent 1, and the compound that acts as a ligand may or may not be added. It is preferable to protect the phenols before the coupling reaction. The protecting group is then removed with a deprotecting agent such as hydrochloric acid, p-toluenesulfonic acid, or the like to give the ligand.

[0081] Examples of basic compounds include sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium tert-butoxide, potassium tert-butoxide, and tripotassium phosphate.

[0082] Examples of palladium catalysts include bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tris(dibenzylideneacetone)(chloroform)dipalladium, palladium chloride, palladium acetate, dichlorobis(acetonitrile)palladium, dichlorobis(benzonitrile)palladium, and allylpalladium chloride dimer.

[0083] Examples of compounds that can serve as ligands for palladium catalysts include phosphine compounds such as tricyclohexylphosphine, tri-tert-butylphosphine, di-tert-butyl(methyl)phosphine, 2-(dicyclohexylphosphino)biphenyl, 2-dicyclohexylphosphino-2'-(dimethylamino)biphenyl, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, and salts of phosphine compounds such as di-tert-butyl(methyl)phosphonium tetrafluoroborate.

[0084] Also, complex compounds of the above phosphine compounds with palladium, such as dichlorobis(tricyclohexylphosphine)palladium, and complex compounds of carbene compounds with palladium, such as {1,3-bis(2,6-diisopropylphenyl)imidazolidene}(3-chloropyridyl)palladium dichloride, may be used as catalysts.

[0085] As the solvent 1, any solvent commonly used in such reactions can be used, but polar solvents such as tetrahydrofuran (THF), dimethoxyethane, 1,4-dioxane, N,N-dimethylformamide (DMF), ethanol, and propanol, and hydrocarbon solvents such as toluene and xylene are preferred, and these may be mixed in any ratio. Furthermore, the solvent may be prepared by adding water to the above solvent, and the mixing ratio of water to solvent is preferably 0 / 100 to 25 / 75.

[0086] Commercially available 3,3'-dibromo-2,2'-dialkoxybiaryls may be used. For example, those produced by a method of lithiating a 2,2'-alkoxybiaryl with an alkyllithium reagent in solvent 2 and then adding, for example, N-bromosuccinimide, or by a method of adding N-bromosuccinimide and ammonium acetate in acetonitrile may also be used.

[0087] Examples of 3,3'-dibromo-2,2'-dialkoxybiaryls include 3,3'-dibromo-2,2'-diisopropoxy-5,5'-dimethyl-1,1'-binaphthyl, 3,3'-dibromo-2,2'-dineopentoxy-5,5'-dimethyl-1,1'-binaphthyl, 3,3'-dibromo-2,2'-dicyclohexoxy-5,5'-dimethyl-1,1'-binaphthyl, 3,3'-dibromo-2,2'-diisopropoxy-5,5'-dimethyl-6,6',7,7',8,8'-hexahydro-1,1'-bi-2-naphthol, and 3,3',6,6'-tetrabromo-2,2'-diisopropoxy-5,5'-dimethyl-1,1'-bi-2-naphthol.

[0088] Solvent 2 includes, for example, diethyl ether, tetrahydrofuran (THF), tert-butyl methyl ether (TBME), and cyclopentyl methyl ether (CPME).

[0089] Examples of alkyllithium reagents include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and lithium diisopropylamide. Activators such as N,N,N',N'-tetramethylethylenediamine (TMEDA) and hexamethylphosphoric acid triamide (HMPA) may be added, and these may be used in solvent amounts.

[0090] The 2,2'-dialkoxybiaryl may be a commercially available product, or may be one produced by alkylating, for example, a 2,2'-dihydroxybiaryl. The alkylation of a 2,2'-dihydroxybiaryl is carried out, for example, by mixing the 2,2'-dihydroxybiaryl, a basic compound, and an alkylating agent in a solvent 3.

[0091] Examples of 2,2'-dihydroxybiaryls include 2,2'-dihydroxybiphenyl, 2,2'-dihydroxy-1,1'-binaphthyl, 5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol, and 6,6'-dibromo-1,1'-bi-2-naphthol.

[0092] Examples of the basic compound include the same basic compounds as those used in the Suzuki-Miyaura coupling reaction of the 3,3'-dibromo-2,2'-dialkoxybiaryls with boronic acids derived from phenols.

[0093] Alkylating agents include, for example, dimethyl sulfate, methyl iodide, dimethyl carbonate, diethyl carbonate, bromopropane, bromobutane, 1-iodopropane, 2-iodopropane, iodoneopentane, iodocyclohexane, and isobutene.

[0094] Examples of the solvent 3 include acetone, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF).

[0095] 2,2'-Dialkoxybiaryls can also be prepared by Suzuki-Miyaura coupling reaction of boronic acids derived from alkoxyaryls with halogenated alkoxyaryls.

[0096] The alkoxyaryls may be commercially available products or may be produced by alkylating a hydroxyaryl. Specifically, the alkoxyaryls can be produced by mixing a hydroxyaryl, a basic compound, and an alkylating agent in the solvent 3.

[0097] Examples of the hydroxyaryl include phenol, p-cresol, m-cresol, and o-xylenol. It is also preferable to use halogenated hydroxyaryl such as 2-bromo-p-cresol as the hydroxyaryl.

[0098] Examples of the basic compound include the same basic compounds as those used in the Suzuki-Miyaura coupling reaction of the 3,3'-dibromo-2,2'-dialkoxybiaryls with boronic acids derived from phenols.

[0099] Examples of the alkylating agent include the same alkylating agents as those used in the production of the 2,2'-dialkoxybiaryls.

[0100] The boronic acids derived from the alkoxyaryls can be synthesized, for example, by lithiating the alkoxyaryl with an alkyllithium reagent in the solvent 2, followed by adding a boronic acid ester.

[0101] Examples of the alkyllithium reagent include the same alkyllithium reagents as those used in the production of the above-mentioned 3,3'-dibromo-2,2'-dialkoxybiaryls.

[0102] Boronic acid esters include, for example, trimethoxyboronic acid, triethoxyboronic acid, and triisopropoxyboronic acid.

[0103] The method for halogenating the alkoxyaryl may be, for example, a method in which a halogenating agent is allowed to act on the alkoxyaryl.

[0104] Examples of halogenating agents include bromine, N-bromosuccinimide, 1,2-dibromoethane, iodine, N-iodosuccinimide, and 1,2-diiodoethane.

[0105] A method for producing 2,2'-dialkoxybiaryls by the Suzuki-Miyaura coupling reaction of a boronic acid derived from an alkoxyaryl with a halogenated alkoxyaryl can be exemplified by adding the solvent 1 to a mixture of these compounds, a basic compound, a palladium catalyst, and a compound that serves as a ligand for the palladium catalyst. These may or may not be dissolved in the solvent, and a compound that serves as a ligand may or may not be added.

[0106] Examples of the basic compound, palladium catalyst, and compound that acts as a ligand for the palladium catalyst include the same compounds as those used in the Suzuki-Miyaura coupling reaction between the 3,3'-dibromo-2,2'-dialkoxybiaryls and boronic acids derived from phenols. The basic compound, palladium catalyst, solvent 1, and optional compound that acts as a ligand for the palladium catalyst used in producing 2,2'-dialkoxybiaryls are preferably the same as the basic compound, palladium catalyst, solvent 1, and optional compound that acts as a ligand for the palladium catalyst used in the Suzuki-Miyaura coupling reaction between the 3,3'-dibromo-2,2'-dialkoxybiaryls and boronic acids derived from phenols.

[0107] Boronic acids derived from phenols can be synthesized, for example, by brominating the corresponding phenols, followed by lithiation with an alkyllithium reagent, followed by the addition of a boronic acid ester. Bromination of phenols is carried out by adding a brominating agent such as N-bromosuccinimide to the phenols in solvent 4. Commercially available brominated phenols may also be used to prepare boronic acids derived from phenols.

[0108] Examples of solvent 4 include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2-trichloroethane, and 1,1,2,2-tetrachloroethane.

[0109] Examples of the alkyllithium reagent include the same alkyllithium reagents as those used in the production of the 3,3'-dibromo-2,2'-dialkoxybiaryls.

[0110] Examples of the boronic acid ester include the same boronic acid esters as those used in the production of boronic acids derived from the above-mentioned alkoxyaryls.

[0111] Phenols are protected, for example, by a conventional method. Examples of protecting groups include tert-butyl, trityl, benzyl, p-methoxybenzyl, methoxymethyl, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, triisopropylsilyl, methanesulfonyl, acetyl, pivaloyl, 2,2,2-trichloroethoxycarbonyl, and allyloxycarbonyl.

[0112] Boronic acids derived from phenols can also be produced by adding the alkyllithium reagent and the boronic acid ester to a phenol, without going through the bromination.

[0113] Commercially available phenols can be used, but in the case of synthesis, they can be obtained, for example, by a copper-catalyzed cross-coupling reaction between carbazoles and aryl halides. Specifically, the solvent 1 is added to a mixture of carbazoles, aryl halides, a basic compound, copper(I) iodide as a catalyst, and a compound that serves as a ligand for the copper catalyst. These may or may not be dissolved in the solvent, and the compound that serves as a ligand may or may not be added. Examples of the basic compound include the same basic compounds as those used in the Suzuki-Miyaura coupling reaction of the 3,3'-dibromo-2,2'-dialkoxybiaryls with boronic acids derived from phenols.

[0114] Phenols can also be obtained by the Suzuki-Miyaura coupling reaction of halogenated carbazoles with arylboronic acids. Specifically, the solvent 1 is added to a mixture of halogenated carbazoles, arylboronic acids, a basic compound, a palladium catalyst, and a compound that acts as a ligand for the palladium catalyst. These may or may not be dissolved in the solvent, and the compound that acts as a ligand may or may not be added.

[0115] Examples of the basic compound, palladium catalyst, and compound that can serve as a ligand for the palladium catalyst include the same compounds as those used in the Suzuki-Miyaura coupling reaction of the 3,3′-dibromo-2,2′-dialkoxybiaryls with boronic acids derived from phenols.

[0116] Examples of halogenated carbazoles include 2,7-dichlorocarbazole, 2,7-dibromocarbazole, 2,7-diiodocarbazole, 3,6-dichlorocarbazole, 3,6-dibromocarbazole, 3,6-diiodocarbazole, 4,5-dichlorocarbazole, 4,5-dibromocarbazole, and 4,5-diiodocarbazole.

[0117] Examples of arylboronic acids include phenylboronic acid, o-methylphenylboronic acid, m-methylphenylboronic acid, p-methylphenylboronic acid, 1-naphthylboronic acid, 2-naphthylboronic acid, 1-anthraceneboronic acid, 2-anthraceneboronic acid, 9-anthraceneboronic acid, 1-phenanthreneboronic acid, 2-phenanthreneboronic acid, 3-phenanthreneboronic acid, 4-phenanthreneboronic acid, 9-phenanthreneboronic acid, 3,5-di-tert-butyl-phenylboronic acid, mesitylboronic acid, 2,4,6-triisopropylphenylboronic acid, 4-methoxyboronic acid, and 4-trifluoromethylphenylboronic acid.

[0118] The arylboronic acids may be prepared by, for example, using hydroxyaryls, protecting the hydroxy group of the hydroxyaryls with a protecting group, followed by bromination and lithiation with an alkyllithium reagent, and then adding a boronate ester. Bromination of hydroxyaryls is carried out by adding a brominating agent such as N-bromosuccinimide to the hydroxyaryls in the solvent 4. Commercially available brominated hydroxyaryls may be used to prepare arylboronic acids.

[0119] Examples of the alkyllithium reagent include the same alkyllithium reagents as those used in the production of the 3,3'-dibromo-2,2'-dialkoxybiaryls.

[0120] Examples of the boronic acid ester include the same boronic acid esters as those used in the production of boronic acids derived from the above-mentioned alkoxyaryls.

[0121] The protection of hydroxyaryls is carried out, for example, according to a conventional method. Examples of the protecting group include the same substituents as those used for protecting phenols.

[0122] Arylboronic acids derived from hydroxyaryls can also be produced by adding the alkyllithium reagent and the boronic acid ester to the hydroxyaryls without going through the bromination.

[0123] Suzuki-Miyaura Coupling Reaction of Boronic Acids Derived from 2,2'-Dialkoxybiaryls with Halogenated Phenols The Suzuki-Miyaura coupling reaction of boronic acids derived from 2,2'-dialkoxybiaryls with halogenated phenols is carried out by adding the solvent 1 to a mixture of these compounds, a basic compound, a palladium catalyst, and a compound that acts as a ligand for the palladium catalyst. These may or may not be dissolved in the solvent, and the ligand compound may or may not be added. It is also preferable to protect the halogenated phenols before this coupling reaction.

[0124] The protecting groups are then removed with a deprotecting agent such as hydrochloric acid and p-toluenesulfonic acid to obtain the ligand. Examples of the basic compound, palladium catalyst, and compound that can serve as a ligand for the palladium catalyst include the same compounds as those used in the Suzuki-Miyaura coupling reaction of 3,3'-dibromo-2,2'-dialkoxybiaryls with boronic acids derived from phenols.

[0125] The 3,3'-dibromo-2,2'-dialkoxybiaryls may be commercially available products, or may be produced by, for example, a method in which a 2,2'-dialkoxybiaryl is lithiated with an alkyllithium reagent in the solvent 2 and then N-bromosuccinimide or the like is added, or a method in which N-bromosuccinimide and ammonium acetate are added in an acetonitrile solvent.

[0126] A boronic acid derived from a 2,2'-dialkoxybiaryl can be synthesized by lithiating a 2,2'-dialkoxybiaryl with an alkyllithium reagent in the solvent 2, followed by adding a boronic acid ester.

[0127] Examples of the alkyllithium reagent include the same alkyllithium reagents as those used in the production of the 3,3'-dibromo-2,2'-dialkoxybiaryls.

[0128] Examples of the boronic acid ester include the same boronic acid esters as those used in the production of boronic acids derived from the above-mentioned alkoxyaryls.

[0129] The 2,2'-dialkoxybiaryl to be used may be a commercially available product, or may be one produced by the above-mentioned method.

[0130] The halogenated phenols are protected, for example, by a conventional method using a protecting group such as tert-butyl, trityl, benzyl, p-methoxybenzyl, methoxymethyl, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, triisopropylsilyl, methanesulfonyl, acetyl, pivaloyl, 2,2,2-trichloroethoxycarbonyl, or allyloxycarbonyl.

[0131] Commercially available halogenated phenols can be used as is, but they can also be synthesized by, for example, the Suzuki-Miyaura coupling reaction of 2-methoxyphenylboronic acids with aryl halides, followed by demethylation and halogenation. Specifically, solvent 1 is added to a mixture of 2-methoxyphenylboronic acids, aryl halides, a basic compound, a palladium catalyst, and a compound that acts as a ligand for the palladium catalyst. These may or may not be dissolved in solvent 1, and the ligand compound may or may not be added. The product can then be synthesized by reacting with a demethylating agent such as boron tribromide, followed by a halogenating agent.

[0132] Examples of 2-methoxyphenylboronic acids include 2-methoxyphenylboronic acid, (2-methoxy-5-methylphenyl)boronic acid, (5-isopropyl-2-methoxyphenyl)boronic acid, 5-tert-butyl-2-methoxyphenylboronic acid, and (2-methoxy-5-trifluorophenyl)boronic acid.

[0133] Examples of aryl halides include chlorobenzene, bromobenzene, iodobenzene, o-bromotoluene, m-bromotoluene, p-bromotoluene, 1-bromonaphthalene, 2-bromonaphthalene, 1-bromoanthracene, 2-bromoanthracene, 9-bromoanthracene, 1-bromophenanthrene, 2-bromophenanthrene, 3-bromophenanthrene, 4-bromophenanthrene, 9-bromophenanthrene, 3,5-di-tert-butylbromobenzene, 2,4,6-triisopropylbromobenzene, bromomesitylene, p-methoxybromobenzene, and p-trifluoromethylbromobenzene.

[0134] Examples of the basic compound, palladium catalyst, and compound that can serve as a ligand for the palladium catalyst include the same compounds as those used in the Suzuki-Miyaura coupling reaction of the 3,3′-dibromo-2,2′-dialkoxybiaryls with boronic acids derived from phenols.

[0135] Examples of the halogenating agent include the same halogenating agents as those used in the halogenation of the alkoxyaryl.

[0136] <Production of transition metal compound [A]> The corresponding transition metal compound [A] can be produced by reacting the ligand prepared by the above method with a metal compound containing M. Specifically, the synthesized ligand is dissolved in a solvent and, if necessary, contacted with a base to prepare an anion, which is then mixed with a metal compound such as a metal halide, metal alkylate, or metal amide at a low temperature and stirred at temperatures ranging from −78°C to room temperature or under reflux for approximately 1 to 48 hours. Solvents commonly used in such reactions can be used, with polar solvents such as diethyl ether and tetrahydrofuran (THF), hydrocarbon solvents such as toluene, and dichloromethane being preferred. Examples of bases used in preparing the anion include metal salts, triethylamine, and pyridine. Examples of metal salts include lithium salts such as n-butyllithium, sodium salts such as sodium hydride, and magnesium salts such as methylmagnesium bromide.

[0137] Depending on the properties of the compound, the corresponding transition metal compound [A] can be synthesized by directly reacting the ligand with the metal compound without first preparing the anion. Furthermore, the metal M in the synthesized transition metal compound can be exchanged with another transition metal by a conventional method. For example, R 1 ~R 9 and R 12 ~R 14 When one or more of the groups are hydrogen atoms, a substituent other than a hydrogen atom can be introduced at any stage of the synthesis.

[0138] Alternatively, the reaction solution of the ligand and the metal compound may be used as it is for polymerization without isolating the transition metal compound.

[0139] <Olefin polymerization catalyst> The olefin polymerization catalyst according to the present invention contains a transition metal compound [A] represented by the general formula (I) above.

[0140] The olefin polymerization catalyst preferably contains, together with the transition metal compound [A], at least one compound [B] selected from the group consisting of an organometallic compound [B-1] and a compound [B-2] that reacts with the transition metal compound [A] to form an ion pair.

[0141] In this specification, an olefin is a hydrocarbon having one or more carbon-carbon double bonds in the molecule.

[0142] As the transition metal compound [A] contained in the olefin polymerization catalyst, the above-mentioned transition metal compound [A] is used.

[0143] The compound [B] preferably used as a constituent component of the olefin polymerization catalyst will be described in detail below.

[0144] [Compound [B]] In terms of polymerization activity, the olefin polymerization catalyst of the present invention preferably further contains, in addition to the transition metal compound [A], at least one compound selected from an organometallic compound [B-1] and a compound [B-2] that reacts with the transition metal compound [A] to form an ion pair.

[0145] The compounds [B-1] and [B-2] will be explained below.

[0146] (organometallic compound [B-1]) Examples of the organometallic compound [B-1] include organoaluminum compounds represented by the following general formula (B-1a), complex alkyl compounds of a metal of Group 1 of the periodic table with aluminum represented by the following general formula (B-1b), and dialkyl compounds of a metal of Group 2 or Group 12 of the periodic table represented by the following general formula (B-1c). Note that the organometallic compound [B-1] does not include organoaluminum oxy compounds [B-2] described below.

[0147] R a p Al(OR b ) q H rY s ···(B-1a) In general formula (B-1a), R a and R b may be the same as or different from each other, and are hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Y is a halogen atom, p is a number such that 0 < p ≤ 3, q is a number such that 0 ≤ q < 3, r is a number such that 0 ≤ r < 3, s is a number such that 0 ≤ s < 3, and p + q + r + s = 3. M 3 AlR c 4···(B-1b) In general formula (B-1b), M 3 is Li, Na or K, and R c is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. R d R e M 4 ···(B-1c) In general formula (B-1c), R d and R e may be the same as or different from each other, and are hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. M 4 is Mg, Zn or Cd.

[0148] Examples of the organoaluminum compound represented by the general formula (B-1a) include the following compounds.

[0149] R a p Al(OR b ) 3-p (where R a and R b may be the same as or different from each other, and are hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number such that 1.5 ≤ p ≤ 3.) The organoaluminum compound represented by R a p AlY 3-p (where R a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y is a halogen atom, and p is preferably a number such that 0 < p < 3.) The organoaluminum compound represented by Ra p AlH 3-p (wherein, R a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number of 2 ≦ p < 3.) and R a p Al(OR b ) q Y s (wherein, R a and R b may be the same or different from each other and are hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y is a halogen atom, p is a number of 0 < p ≦ 3, q is a number of 0 ≦ q < 3, s is a number of 0 ≦ s < 3, and p + q + s = 3.) and an organoaluminum compound represented by

[0150] Examples of the organoaluminum compound represented by the general formula (B-1a) include tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; tri-branched chain alkylaluminum such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminum such as triphenylaluminum and tritolylaluminum; dialkylaluminum hydride such as diisobutylaluminum hydride; (i-C4H9) xAl y (C5H 10 ) z (wherein x, y, and z are positive numbers, and z≧2x), and other trialkenylaluminums such as triisoprenylaluminum; alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, and isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, and butylaluminum sesquibutoxide; R a 2.5 Al(OR b ) 0.5 Partially alkoxylated alkylaluminum having an average composition represented by the formula a and R b may be the same or different and are hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms); dialkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-tert-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-tert-butyl-4-methylphenoxide), and isobutylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; partially halogenated alkylaluminums, such as alkylaluminum dihalides, such as ethylaluminum dichloride, propylaluminum dichloride, and butylaluminum dibromide; dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Other partially hydrogenated alkylaluminums, such as ethylaluminum dihydride and alkylaluminum dihydrides, such as propylaluminum dihydride; Included are partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

[0151] Compounds similar to the organoaluminum compound represented by general formula (B-1a) can also be used, such as organoaluminum compounds in which two or more aluminum compounds are bonded via nitrogen atoms, such as (C2H5)2AlN(C2H5)Al(C2H5)2.

[0152] Examples of the compound represented by the general formula (B-1b) include LiAl(C2H5)4, LiAl(C7H 15 )4 can be mentioned.

[0153] Examples of the compound represented by the general formula (B-1c) include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butylethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc, diisobutyl zinc, bis(pentafluorophenyl) zinc, dimethyl cadmium, and diethyl cadmium.

[0154] In addition, as the organometallic compound [B-1], methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, etc. can also be used.

[0155] A compound that forms the organoaluminum compound in the polymerization system, such as a combination of an aluminum halide and an alkyllithium, or a combination of an aluminum halide and an alkylmagnesium, can also be used as the organometallic compound [B-1].

[0156] The organometallic compounds [B-1] may be used singly or in combination of two or more. (Compound [B-2] that reacts with transition metal compound [A] to form an ion pair) Examples of the compound [B-2] (hereinafter also referred to as "ionizing ionic compound") that reacts with the transition metal compound [A] to form an ion pair include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in, for example, JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and U.S. Pat. No. 5,321,106. Further examples include heteropoly compounds and isopoly compounds.

[0157] Examples of the Lewis acid include a compound represented by BR3 (R is fluorine or a phenyl group which may have a substituent such as fluorine, a methyl group, or a trifluoromethyl group.) Examples of the compound include trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron, and tris(3,5-dimethylphenyl)boron.

[0158] Examples of the ionic compound include compounds represented by the following general formula (IV).

[0159] [ka]

[0160] (In general formula (IV), R 19 is H + , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, or a ferrocenium cation having a transition metal, and R 20 ~R 23 may be the same or different and are organic groups, preferably aryl groups or substituted aryl groups.

[0161] Examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0162] Examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri(n-butyl)ammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.

[0163] Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0164] R 19 As the cation, a carbonium cation and an ammonium cation are preferred, and a triphenylcarbonium cation, an N,N-dimethylanilinium cation, and an N,N-diethylanilinium cation are more preferred.

[0165] Ionic compounds also include, for example, trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0166] Examples of the trialkyl-substituted ammonium salts include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(m,m-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)boron, and tri(n-butyl)ammonium tetra(o-tolyl)boron.

[0167] Examples of the N,N-dialkylanilinium salt include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N,2,4,6-pentamethylanilinium tetra(phenyl)boron.

[0168] Examples of the dialkylammonium salt include di(1-propyl)ammonium tetra(pentafluorophenyl)boron and dicyclohexylammonium tetra(phenyl)boron.

[0169] Further examples of the ionic compound include triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following formula (V) or (VI):

[0170] [ka]

[0171] (In formula (V), Et represents an ethyl group.)

[0172] [ka]

[0173] (In formula (VI), Et represents an ethyl group.)

[0174] Examples of borane compounds, which are ionizable ionic compounds (compound [B-2]), include decaborane; salts of anions such as bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, and bis[tri(n-butyl)ammonium]dodecachlorododecaborate; and salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydridedodecaborate)cobaltate(III) and bis[tri(n-butyl)ammonium]bis(dodecahydridedodecaborate)nickelate(III).

[0175] Examples of carborane compounds, which are ionizable ionic compounds, include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, and undecahydride-7,8-dimethyl- 7,8-Dicarbaundecaborane, Dodecahydride-11-methyl-2,7-dicarbaundecaborane, Tri(n-butyl)ammonium 1-carbadecaborate, Tri(n-butyl)ammonium 1-carbaundecaborate, Tri(n-butyl)ammonium 1-carbadodecaborate, Tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, Tri(n-butyl)ammonium bromo-1-carbadodecaborate, Tri(n-butyl)ammonium 6 -carbadecaborate, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 7-carbaundecaborate, tri(n-butyl)ammonium 7,8-dicarbaundecaborate, tri(n-butyl)ammonium 2,9-dicarbaundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate Salts of anions such as undecaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate; Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbanonaborate)ferrate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)nickelate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cuprate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)aurate(III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbandecaborate)ferrate salts of metal carborane anions such as tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboxamdecaborate)chromate(III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboxamdecaborate)cobaltate(III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)chromate(III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)manganate(IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)cobaltate(III), and bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)nickelate(IV).

[0176] Heteropoly compounds, which are examples of ionized ionic compounds, are compounds containing an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. Examples of heteropoly compounds include phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphotungstic acid, germanotungstic acid, tintungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid, phosphomolybdoniobic acid, and salts of these acids. Examples of the salts include salts of the acids with metals of Group 1 or 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.

[0177] Isopoly compounds, which are examples of ionized ionic compounds, are compounds composed of metal ions of one type of atom selected from vanadium, niobium, molybdenum, and tungsten, and can be considered to be molecular ionic species of metal oxides. Examples of isopoly compounds include vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. Examples of the salts include salts of the acids with metals from Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.

[0178] The compound [B-2] may be used singly or in combination of two or more.

[0179] The olefin polymerization catalyst may contain the transition metal compound [A], at least one compound [B] selected from the group consisting of an organometallic compound [B-1] and a compound [B-2], and, if necessary, a support [C] as follows:

[0180] [Carrier [C]] The carrier [C] used in the present invention is an inorganic or organic compound, and is a granular or fine particle solid. By supporting the transition metal compound [A] and compound [B] on the carrier [C], a polymer with good morphology can be obtained.

[0181] The inorganic compound is preferably a porous oxide, an inorganic halide, clay, a clay mineral, an ion-exchangeable layered compound, or a solid organoaluminum oxy-compound.

[0182] Examples of the porous oxide that can be used include SiO2, Al2O3, MgO, ZrO, TiO2, BO3, CaO, ZnO, BaO, and ThO2, as well as composites or mixtures containing these, and further examples of natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-VO5, SiO2-Cr2O3, and SiO2-TiO2-MgO. Of these, porous oxides containing SiO2 and / or Al2O3 as the main component are preferred.

[0183] The porous oxide may contain small amounts of carbonates, sulfates, nitrates, and oxides such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, and Li2O.

[0184] The properties of such porous oxides vary depending on the type and manufacturing method, but the porous oxides preferably used in the present invention have 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 700m2 / g, and the pore volume is in the range of 0.3 to 3.0 cm 3 / g range. Such porous oxides are calcined at 100 to 1000°C, preferably 150 to 700°C, as required, before use.

[0185] Examples of inorganic halides that can be used include MgCl, MgBr, MnCl, and MnBr. The inorganic halides may be used as they are or may be pulverized using a ball mill or a vibration mill. Alternatively, the inorganic halides may be dissolved in a solvent such as alcohol and then precipitated into fine particles using a precipitating agent.

[0186] The clay is usually composed mainly of clay minerals. The ion-exchangeable layered compounds are compounds having a crystalline structure in which planes formed by ionic bonds or the like are stacked in parallel with weak bonding forces, and the ions they contain are exchangeable. Most clay minerals are ion-exchangeable layered compounds. These clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products, and artificially synthesized compounds can also be used.

[0187] Examples of clays, clay minerals, or ion-exchangeable layered compounds include ionic crystalline compounds having layered crystal structures such as hexagonal close packing type, antimony type, CdCl2 type, and CdI2 type.

[0188] Furthermore, examples of clays and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, and halloysite. Examples of ion-exchange layered compounds include crystalline acid salts of polyvalent metals such as α-Zr(HAsO)·H0, α-Zr(HPO), α-Zr(KPO 3H0, α-Ti(HPO), α-Ti(HAsO)·H0, α-Sn(HPO), H0, γ-Zr(HPO), γ-Ti(HPO), and γ-Ti(NHPO).

[0189] Such clays, clay minerals, or ion-exchangeable layered compounds preferably have a pore volume of 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g, having a radius of 20 Å or more, as measured by mercury intrusion porosimetry. Here, the pore volume is measured by mercury intrusion porosimetry using a mercury porosimeter for pores with a radius of 20 to 30,000 Å.

[0190] When a carrier having a pore volume of less than 0.1 cc / g with a radius of 20 Å or more is used, it tends to be difficult to obtain high polymerization activity.

[0191] It is also preferable to subject the clay and clay minerals used in the present invention to chemical treatment. Chemical treatments include surface treatments that remove impurities from the surface and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment. Acid treatment not only removes surface impurities but also increases the surface area by eluting cations such as Al, Fe, and Mg in the crystalline structure. Alkali treatment destroys the crystalline structure of the clay, resulting in structural changes. Furthermore, salt treatment and organic treatment form ionic complexes, molecular complexes, organic derivatives, etc., which can change the surface area and interlayer distance.

[0192] The ion-exchangeable layered compound used in the present invention may be a layered compound in which the interlayer spacing is expanded by utilizing the ion exchange property and exchanging the exchangeable ions between the layers with other large, bulky ions. Such bulky ions act as supports supporting the layered structure and are usually called pillars. The introduction of another substance between the layers of a layered compound in this manner is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (where R is a hydrocarbon group, etc.), and [Al 13 O4(OH) 24 ] 7+ , [Zr4(OH) 14 ] 2+ , [Fe3O(OCOCH3)6] + Examples of suitable pillars include metal hydroxide ions such as those mentioned above. These compounds may be used alone or in combination of two or more. When intercalating these compounds, polymers obtained by hydrolysis of metal alkoxides (where R is a hydrocarbon group, etc.) such as Si(OR)4, Al(OR)3, and Ge(OR)4, and colloidal inorganic compounds such as SiO2, may also be present. Examples of suitable pillars include oxides produced by intercalating the metal hydroxide ions between layers and then dehydrating them with heat.

[0193] The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as is, or may be used after treatment such as ball milling or sieving. They may also be used after newly adding and adsorbing water or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more.

[0194] The solid organoaluminum oxy-compound is a solid component obtained by insolubilizing an organoaluminum oxy-compound, and can be obtained by the methods described in JP-A-11-140113, JP-A-2000-38410, JP-A-2000-95810, WO 2010 / 55652, etc.

[0195] As mentioned above, the carrier [C] is an inorganic or organic compound, and examples of the organic compound include granular or fine particle solids with particle sizes in the range of 10 to 300 μm. Specific examples include (co)polymers produced mainly from an α-olefin having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or (co)polymers produced mainly from vinylcyclohexane or styrene, and modified products thereof.

[0196] The olefin polymerization catalyst contains the transition metal compound [A], preferably the compound [B], and, if necessary, a support [C]. In addition to these, the catalyst may also contain, if necessary, a specific organic compound component [D] described below.

[0197] [Organic compound component [D]] The organic compound component [D] is used as needed for the purpose of improving the polymerization performance (e.g., catalytic activity) of the olefin polymerization catalyst and the physical properties of the resulting polymer (e.g., increasing the molecular weight of the resulting polymer). Examples of such organic compounds include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

[0198] The alcohols and phenolic compounds are generally selected from the group consisting of R 24 -OH, where R 24 is a hydrocarbon group having 1 to 50 carbon atoms (6 to 50 carbon atoms in the case of phenols) or a halogenated hydrocarbon group having 1 to 50 carbon atoms (6 to 50 carbon atoms in the case of phenols).

[0199] As for alcohols, R 24 The phenolic compound is preferably one in which the α,α'-positions of the hydroxyl group are substituted with a hydrocarbon having 1 to 20 carbon atoms.

[0200] The carboxylic acid is usually R 25The one represented by -COOH is used. 25 is a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and is preferably a halogenated hydrocarbon group having 1 to 50 carbon atoms.

[0201] As the phosphorus compound, phosphoric acids having a P-O-H bond, phosphates having a P-O-R or P=O bond, and phosphine oxide compounds are preferably used.

[0202] <Method of producing olefin polymer> In the method for producing an olefin polymer according to the present invention, an olefin polymer is produced by homopolymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst. As mentioned above, in this specification, an olefin refers to a hydrocarbon having one or more carbon-carbon double bonds in the molecule.

[0203] In the method for producing an olefin polymer, olefin homopolymerization or olefin copolymerization is carried out in the presence of the olefin polymerization catalyst. The copolymerization of olefins requires that at least one monomer is an olefin, and two or more olefins may be copolymerized, or an olefin may be copolymerized with a monomer other than an olefin. Specifically, examples of olefin copolymerization include copolymerization of two or more olefins and copolymerization of an olefin with a monomer other than an olefin.

[0204] In the polymerization, the components constituting the catalyst of the present invention may be used in any manner and added to the polymerization vessel in any order. For example, the following methods may be mentioned. (1) A method in which the transition metal compound [A] is added alone to a polymerization reactor. (2) A method in which the transition metal compound [A] and the compound [B] are added to a polymerization reactor in any order. (3) A method in which a catalyst component in which a transition metal compound [A] is supported on a carrier [C] and a compound [B] are added to a polymerization reactor in any order. (4) A method in which a catalyst component in which the compound [B] is supported on the carrier [C] and a transition metal compound [A] are added to a polymerization reactor in any order. (5) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] are supported on a carrier [C] is added to a polymerization reactor. (6) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] are supported on a carrier [C], and the compound [B] are added to a polymerization reactor in any order. In this case, the compounds [B] may be the same or different. (7) A method in which a catalyst component in which the compound [B] is supported on the carrier [C] and a transition metal compound [A] are added to a polymerization reactor in any order. (8) A method in which a catalyst component in which compound [B] is supported on a carrier [C], a transition metal compound [A], and compound [B] are added to a polymerization reactor in any order. In this case, the compounds [B] may be the same or different. (9) A method in which a component in which a transition metal compound [A] is supported on a carrier [C] and a component in which a compound [B] is supported on a carrier [C] are added to a polymerization reactor in any order. (10) A method in which a component in which a transition metal compound [A] is supported on a carrier [C], a component in which a compound [B] is supported on a carrier [C], and a compound [B] are added to a polymerization reactor in any order. In this case, the compounds [B] may be the same or different. (11) A method in which the transition metal compound [A], the compound [B], and the organic compound component [D] are added to a polymerization reactor in any order. (12) A method in which the compound [B] and the organic compound component [D] are contacted in advance, and the transition metal compound [A] are added to a polymerization reactor in any order. (13) A method in which the compound [B], the organic compound component [D] supported on the carrier [C], and the transition metal compound [A] are added to a polymerization reactor in any order. (14) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] have been contacted in advance, and an organic compound component [D] are added to a polymerization reactor in any order. (15) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] have been contacted in advance, compound [B], and organic compound component [D] are added to a polymerization reactor in any order. In this case, the compounds [B] may be the same or different. (16) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] have been previously contacted, and a component in which a compound [B] and an organic compound component [D] have been previously contacted, are added to a polymerization reactor in any order. In this case, the compounds [B] may be the same or different. (17) A method in which a transition metal compound [A] supported on a carrier [C], a compound [B], and an organic compound component [D] are added to a polymerization reactor in any order. (18) A method in which a component in which a transition metal compound [A] is supported on a carrier [C] and a component in which a compound [B] and an organic compound component [D] are previously contacted are added to a polymerization reactor in any order. (19) A method in which a catalyst component obtained by previously contacting a transition metal compound [A], a compound [B] and an organic compound component [D] in any order is added to a polymerization reactor. (20) A method in which a catalyst component obtained by previously contacting a transition metal compound [A], a compound [B] and an organic compound component [D] in any order, and compound [B] are added to a polymerization reactor in any order. In this case, the compounds [B] may be the same or different. (21) A method in which a catalyst in which a transition metal compound [A], a compound [B] and an organic compound component [D] are supported on a carrier [C] is added to a polymerization reactor. (22) A method in which a catalyst component comprising a transition metal compound [A], a compound [B], and an organic compound component [D] supported on a carrier [C], and compound [B] are added to a polymerization reactor in any order. In this case, the compounds [B] may be the same or different.

[0205] The solid catalyst component in which the transition metal compound [A] is supported on the support [C], or the solid catalyst component in which the transition metal compound [A] and the compound [B] are supported on the support [C], may have an olefin prepolymerized thereon, or the prepolymerized solid catalyst component may have another catalyst component supported thereon. The compound [B] may be one type or two or more types.

[0206] In the present invention, polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. Examples of inert hydrocarbon media used in liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof. The olefin (monomer) itself to be (co)polymerized can also be used as the solvent.

[0207] When olefin polymerization is carried out using the above-mentioned olefin polymerization catalyst, the transition metal compound [A] is usually used in an amount of 1×10 per liter of reaction volume. -12 ~1×10 -2 mol, preferably 1 x 10 -10 ~1×10 -3 It is used in molar amounts.

[0208] The organometallic compound [B-1] is used in an amount such that the molar ratio ([B-1] / M) of the organometallic compound [B-1] to all transition metal atoms (M) in the transition metal compound [A] is usually 0.01 to 200,000, preferably 0.05 to 100,000. The compound [B-2] that reacts with the transition metal compound [A] to form an ion pair is used in an amount such that the molar ratio ([B-2] / M) of the compound [B-2] to all transition metal atoms (M) in the transition metal compound [A] is usually 1 to 1,000, preferably 1 to 500.

[0209] When compound [B] is an organometallic compound [B-1], organic compound component [D] is used in an amount such that the molar ratio of organic compound component [D] to organometallic compound [B-1] ([D] / [B-1]) is usually 0.01 to 100, preferably 0.1 to 50. When compound [B] is compound [B-2], organic compound component [D] is used in an amount such that the molar ratio of organic compound component [D] to compound [B-2] ([D] / [B-2]) is usually 0.01 to 100, preferably 0.1 to 50.

[0210] The polymerization temperature of olefins using such an olefin polymerization catalyst is usually in the range of −50 to +200° C., preferably 0 to 170° C. The polymerization pressure is usually normal pressure to 100 kgf / cm. 2 -G (gauge pressure), preferably normal pressure to 50 kgf / cm 2 The polymerization reaction is carried out under the conditions of -G (gauge pressure), and can be carried out in any of batch, semi-continuous, and continuous systems. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

[0211] The molecular weight of the resulting olefin polymer can be controlled by adding hydrogen to the polymerization system or by changing the polymerization temperature. Furthermore, it can also be controlled by the amount of compound [B] used.

[0212] The olefin that can be polymerized by the olefin polymerization catalyst of the present invention is not particularly limited, but includes linear or branched α-olefins having 2 to 30, preferably 2 to 20, carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, and vinylcyclohexane; Examples of non-conjugated polyenes include cyclic or linear non-conjugated diolefins having 4 to 30, preferably 4 to 20, carbon atoms and two or more carbon-carbon double bonds per molecule, such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, and 7-methyl-1,6-octadiene, as well as trienes such as 4-ethylidene-8-methyl-1,7-nonadiene and 5,9-dimethyl-1,4,8-decatriene. Further examples of the olefin include aromatic vinyl compounds, such as mono- or polyalkylstyrenes, such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene; Examples include 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene, and divinylbenzene.

[0213] The olefin polymerization catalyst can also copolymerize an olefin with another monomer. The other monomer may be any monomer other than an olefin, and is not particularly limited, but examples thereof include a monomer having a polar group (e.g., a carbonyl group, a hydroxyl group, an ether bond group, etc.) and a polymerizable carbon-carbon double bond in the molecule (hereinafter also referred to as a "polar group-containing monomer").

[0214] Examples of polar group-containing monomers include acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, 17-octadecenoic acid, 18-nonadecenoic acid, 19-eicosenoic acid, 2 0-Henicosenoic acid, 21-docosenoic acid, 22-tricosenoic acid, methacrylic acid, 2-methylpentenoic acid, 2,2-dimethyl-3-butenoic acid, 2,2-dimethyl-4-pentenoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 2,6-heptadienoic acid, 2-(4-isopropylbenzylidene)-4-pentenoic acid, allylmalonic acid, 2-(10-undecenyl)malonic acid, fumaric acid, itaconic acid, bicyclo[2. unsaturated carboxylic acids such as 2.1]-5-heptene-2-carboxylic acid and bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid, and metal salts thereof such as sodium salts, potassium salts, lithium salts, zinc salts, magnesium salts, and calcium salts; unsaturated carboxylic acid esters such as methyl esters, ethyl esters, n-propyl esters, isopropyl esters, n-butyl esters, isobutyl esters, and (5-norbornen-2-yl) esters of these unsaturated carboxylic acids (when the unsaturated carboxylic acid is a dicarboxylic acid, they may be monoesters or diesters); and unsaturated carboxylic acid amides such as amides and N,N-dimethylamides of these unsaturated carboxylic acids (when the unsaturated carboxylic acid is a dicarboxylic acid, they may be monoamides or diamides); Unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, allylsuccinic anhydride, isobutenylsuccinic anhydride, (2,7-octadien-1-yl)succinic anhydride, tetrahydrophthalic anhydride, and bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic anhydride; vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; Halogenated olefins such as vinyl chloride, vinyl fluoride, vinyl bromide, vinyl iodide, allyl bromide, allyl chloride, allyl fluoride, and allyl iodide; silylated olefins such as allyltrimethylsilane, diallyldimethylsilane, 3-butenyltrimethylsilane, allyltriisopropylsilane, and allyltriphenylsilane; unsaturated nitriles such as acrylonitrile, 2-cyanobicyclo[2.2.1]-5-heptene, and 2,3-dicyanobicyclo[2.2.1]-5-heptene; Unsaturated alcohol compounds such as allyl alcohol, 3-butenol, 4-pentenol, 5-hexenol, 6-hebutenol, 7-octenol, 8-nonenol, 9-decenol, 10-undecenol, 11-dodecenol, and 12-tridecenol, and unsaturated esters thereof such as acetate esters, benzoate esters, propionate esters, caproate esters, caprate esters, laurate esters, and stearates; Substituted phenols such as vinylphenol and allylphenol; unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether, allyl methyl ether, allyl propyl ether, allyl butyl ether, allyl methallyl ether, methoxystyrene, ethoxystyrene, and allyl anisole; Unsaturated epoxides such as butadiene monoxide, 1,2-epoxy-7-octene, and 3-vinyl-7-oxabicyclo[4.1.0]heptane; Unsaturated aldehydes such as acrolein and undecenal, and unsaturated acetals thereof such as dimethyl acetal and diethyl acetal; unsaturated ketones such as methyl vinyl ketone, ethyl vinyl ketone, allyl methyl ketone, allyl ethyl ketone, allyl propyl ketone, allyl butyl ketone, and allyl benzyl ketone, and unsaturated acetals thereof such as dimethyl acetal and diethyl acetal; Unsaturated thioethers such as allyl methyl sulfide, allyl phenyl sulfide, allyl isopropyl sulfide, allyl n-propyl sulfide, and 4-pentenyl phenyl sulfide; Unsaturated sulfoxides such as allylphenyl sulfoxide; Examples thereof include unsaturated sulfones such as allylphenyl sulfone; unsaturated phosphines such as allyldiphenylphosphine; and unsaturated phosphine oxides such as allyldiphenylphosphine oxide.

[0215] Furthermore, examples of the polar group-containing monomer include vinylbenzyl acetate, hydroxystyrene, methyl 4-(3-butenyloxy)benzoate, methoxystyrene, ethoxystyrene, allyl trifluoroacetate, o-chlorostyrene, p-chlorostyrene, glycidyl acrylate, allyl glycidyl ether, (2H-perfluoropropyl)-2-propenyl ether, linalool oxide, 3-allyloxy-1,2-propanediol, 2-(allyloxy)ethanol, N-allylmorpholine, allylglycine, N-vinylpyrrolidone, allyltrichlorosilane, acryltrimethylsilane, allyldimethyl(diisopropylamino)silane, 7-octenyltrimethoxysilane, allyloxytrimethylsilane, and allyloxytriphenylsilane, which can be copolymerized with olefins using the olefin polymerization catalyst of the present invention.

[0216] Further examples of other monomers include functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, and p-chlorostyrene. [Example]

[0217] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples.

[0218] [Identification method] The structures of the compounds obtained in the synthesis examples and examples are as follows: 1Identification was performed using H-NMR spectra (400 MHz, JEOL Ltd., JNM-ECZ400S / L1 model or 500 MHz, Bruker Biospin Ltd., AVANCE NEO cryo-500 model), FD-MS spectra (JEOL Ltd., JMS-T200GC), and GC-MS spectra (Shimadzu Corporation, GC-2030 / GCMS-QP2020 NX).

[0219] [Synthesis Example 1] A thoroughly dried 300 mL three-neck flask was charged with 5.00 g (0.027 mol) of 2-bromo-p-cresol, 15.9 g (0.093 mol) of 2-iodopropane, 7.39 g (0.054 mmol) of potassium carbonate, and 20 mL of tetrahydrofuran (THF) under a nitrogen atmosphere and stirred at reflux for 72 hours. After the reaction, the mixture was extracted twice with ethyl acetate. The organic layer was washed once with brine (saturated aqueous sodium chloride solution) and dried over sodium sulfate. The dried solution was concentrated using a rotary evaporator to give 5.90 g of compound (1) (96% yield, colorless oily liquid). The product was confirmed by GC-MS spectroscopy.

[0220] [ka]

[0221] [Synthesis Example 2] A thoroughly dried 200 mL three-neck flask was charged with 2.91 g (0.013 mol) of compound (1) and 40 mL of dehydrated diethyl ether under a nitrogen atmosphere and cooled to -78 °C with dry ice / acetone. While still cooled, 11.1 mL (0.018 mol) of a 1.59 M n-butyllithium hexane solution was slowly added. After the addition, the dry ice / acetone was removed and the reaction was allowed to proceed for 2 hours while slowly returning to room temperature. The solution was then cooled again to -78 °C with dry ice / acetone, and 3.58 g (0.019 mol) of triisopropyl borate was quickly added. The reaction was allowed to proceed for 15 hours while slowly returning to room temperature. After the reaction, the reaction was quenched by adding 20 mL of 2 N hydrochloric acid and transferred to a separatory funnel. The mixture was extracted three times with diethyl ether, and the resulting organic layer was dried over sodium sulfate. The resulting white solid, primarily consisting of compound (2), was concentrated on a rotary evaporator and used directly in the next reaction.

[0222] [ka]

[0223] [Synthesis Example 3] In a thoroughly dried 200 mL three-neck flask, 2.42 g (10.6 mol) of compound (1), 2.46 g of the crude product containing the synthesized compound (2), 4.48 g (21.1 mmol) of potassium phosphate tribasic, 23.7 mg (0.11 mmol) of palladium(II) acetate, 86.6 mg (0.21 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (Sphos), and 40 mL of THF were added under a nitrogen atmosphere and stirred. Eight mL of water, previously bubbled with nitrogen, was added dropwise while monitoring the internal temperature. After the temperature had subsided, the temperature was raised to 80 °C and stirred for an additional 2 hours. After the reaction, a portion of the solution was evaporated, followed by extraction three times with ethyl acetate. The organic layer was washed with brine and dried over sodium sulfate. The dried solution was concentrated using a rotary evaporator and purified using a silica gel column (hexane:ethyl acetate=10:1) to obtain 2.83 g of compound (3) (colorless viscous liquid, 90% yield). The target product was confirmed by measuring the GC-MS spectrum.

[0224] [ka]

[0225] [Synthesis Example 4] In a thoroughly dried 100 mL three-neck flask, 298.4 mg (1.00 mmol) of compound (3), 5.0 mL of dehydrated acetonitrile, and 15.42 mg (0.20 mmol) of ammonium acetate were added and stirred under a nitrogen atmosphere. 373.8 mg (2.1 mmol) of N-bromosuccinimide was added to the solution and reacted at room temperature for 15 hours. After the reaction, the mixture was quenched by adding brine and transferred to a separatory funnel. Extraction was performed three times with ethyl acetate, and the resulting organic layer was dried over sodium sulfate. The dried solution was concentrated using a rotary evaporator and purified using a silica gel column (hexane:methylene chloride = 5:1) to obtain 196.0 mg of compound (4) (white powder, 43% yield). 1H NMR(400MHz,CDCl3,δ in ppm)7.37(dd,J=2.2,0.7Hz,2H),7.27(dd,J=2.2,0.7Hz,2H),3.92-3.86(m,2H),2.29(s,6H),1.08(d,J=6.3Hz,12H).

[0226] [ka]

[0227] [Synthesis Example 5] A thoroughly dried 200 mL three-neck flask was charged with 5.00 g (0.027 mol) of 2-bromo-p-cresol and 50 mL of dichloromethane under a nitrogen atmosphere and cooled in an ice bath. To the solution, 6.10 mL (35.9 mmol) of diisopropylethylamine (DIPEA) was added, followed by the dropwise addition of 2.50 mL (33.2 mmol) of chloromethyl methyl ether (MOMCl) over 4 minutes via syringe. After the dropwise addition, the mixture was stirred for 2.5 hours under ice bath cooling, then the ice bath was removed and the mixture was stirred at room temperature for 1.5 hours. After the reaction, the solution was poured into cold water and separated. The aqueous layer was extracted with dichloromethane. The organic layer was dried over sodium sulfate. The dried solution was concentrated using a rotary evaporator and purified using a silica gel column (hexane:ethyl acetate = 19:1) to obtain 6.03 g of compound (5) (colorless liquid, 98% yield). The product was confirmed by GC-MS spectroscopy. MOM in compound (5) means a methoxymethyl group.

[0228] [ka]

[0229] [Synthesis Example 6] In a thoroughly dried 200 mL three-neck flask, 6.03 g (26.1 mmol) of compound (5), 1.00 g (5.25 mmol) of copper(I) iodide, 60 mL of toluene, 7.51 g (26.7 mmol) of 3,6-di-tert-butylcarbazole, and 17.3 g (81.5 mmol) of tripotassium phosphate were added and stirred under a nitrogen atmosphere. 0.96 mL (8.93 mmol) of N,N-dimethylethyleneamine (DMEDA) was added and stirred under reflux for 164 hours. After the reaction, the solution was cooled to room temperature, diluted with 75 mL of THF, and filtered. The solution was concentrated on a rotary evaporator, purified on a silica gel column (hexane:ethyl acetate = 19:1), and concentrated on a rotary evaporator. 10 mL of acetonitrile was added and dissolved by heating. The resulting solution was slowly cooled to 0 °C for crystallization. The resulting crystals were filtered, washed with cold acetonitrile (5 mL × 2), and dried under reduced pressure to obtain 6.71 g of compound (6) (white solid, 60% yield). The product was confirmed by measuring the GC-MS spectrum.

[0230] [ka]

[0231] [Synthesis Example 7] In a thoroughly dried 100 mL three-neck flask, 600.0 mg (1.40 mmol) of compound (6) and 10 mL of deoxygenated tetrahydrofuran were added under a nitrogen atmosphere and transferred to a dry ice / acetone bath for cooling. 0.92 mL (1.47 mmol) of a 1.6 M n-butyllithium hexane solution was slowly added dropwise, and the flask was then transferred to an ice bath and reacted for 1.5 hours. After the reaction, the flask was transferred to a dry ice / acetone bath again and cooled to -78 °C. Then, 152.4 mg (1.47 mmol) of trimethoxyborane was quickly added, transferred to an ice bath, and reacted for 1.5 hours. Then, under a nitrogen atmosphere, 286.7 mg (0.63 mmol) of compound (4), 592.9 mg (2.79 mmol) of tripotassium phosphate, 3.1 mg (0.014 mmol) of palladium(II) acetate, 11.5 mg (0.028 mmol) of Sphos, and 15 mL of THF were added to a reaction vessel and stirred. 5 mL of water, which had been previously bubbled with nitrogen, was added dropwise while monitoring the internal temperature. After the temperature had subsided, the mixture was heated to 80 °C and stirred for an additional 18 hours. After the reaction, the mixture was extracted three times with ethyl acetate, and the resulting organic layer was dried over sodium sulfate. The crude product obtained by concentration on a rotary evaporator was purified on a silica gel column (hexane:methylene chloride = 1:2) to obtain 438.7 mg of compound (7) (white powder, 61% yield).

[0232] 1 H NMR(400MHz,CDCl3,δ in ppm)8.13(d,J=1.5Hz,4H),7.49(d,J=1.7Hz,2H),7.47(d,J=2.0Hz,4H),7.36(s,2H),7.31(s,2H),7.29(s,2H)7.27(d,J=2.0Hz, 2H),7.20(d,J=2.2Hz,2H),4.31(s,4H),3.90-3.83(m,2H),2.49(s,6H),2.41(s,6H),2.40(s,6H),1.47(s,36H),0.88(br,12H).

[0233] [ka]

[0234] [Synthesis Example 8] A thoroughly dried 100 mL three-neck flask was charged with 388.7 mg (0.34 mmol) of compound (7) and 10 mL of dichloromethane under a nitrogen atmosphere, and the flask was then cooled in an ice bath. 10 mL of a 4 M hydrogen chloride dioxane solution was added, and the mixture was stirred at room temperature for 15 hours. After the reaction, the mixture was quenched with saturated aqueous sodium bicarbonate, extracted four times with methylene chloride, and the resulting organic layer was dried over sodium sulfate. The white solid obtained by concentration on a rotary evaporator was purified on a silica gel column (hexane:methylene chloride = 1:1) to give 206.8 mg of compound (8) (white powder, 58% yield). 1 H NMR(400MHz,CDCl3,δ in ppm)8.12(s,4H),7.40(d,J=8.5Hz,4H),7.31(s,2H),7.28(s,4H),7.22(s,2H),7.10(d, J=8.5Hz,4H),3.83-3.76(m,2H),2.39(s,6H),2.37(s,6H),1.44(s,36H),0.80(br,12H).

[0235] [ka]

[0236] [Synthesis Example 9] A thoroughly dried 300 mL three-neck flask was charged with 2.50 g (7.34 mmol) of 3',5'-di-tert-butyl-2-(methoxymethoxy)-5-methyl-1,1'-biphenyl and 100 mL of deoxygenated tetrahydrofuran under a nitrogen atmosphere and then transferred to a dry ice / acetone bath for cooling. 4.82 mL (7.71 mmol) of a 1.6 M n-butyllithium hexane solution was slowly added dropwise, and the flask was then transferred to an ice bath and reacted for 1.5 hours. After the reaction, the flask was again transferred to a dry ice / acetone bath and cooled to -78 °C. 801.0 mg (7.71 mmol) of trimethoxyborane was quickly added, and the flask was then transferred to an ice bath and reacted for 2 hours. Next, under a nitrogen atmosphere, 1.51 g (3.3 mmol) of compound (4), 3.12 g (14.7 mmol) of tripotassium phosphate, 16.5 mg (0.073 mmol) of palladium(II) acetate, 60.3 mg (0.15 mmol) of Sphos, and 50 mL of THF were added to a reaction vessel and stirred. 30 mL of water, which had been previously bubbled with nitrogen, was added dropwise while monitoring the internal temperature. After the temperature had subsided, the mixture was heated to 70 °C and stirred for an additional 18 hours. After the reaction, the mixture was extracted three times with ethyl acetate, and the resulting organic layer was dried over sodium sulfate. The crude product obtained by concentration on a rotary evaporator was purified on a silica gel column (hexane:ethyl acetate = 12:1) to obtain 3.34 g of crude product, mainly consisting of compound (9) (white powder, 104% yield). This was used in the next reaction without further purification. MOM in compound (9) means a methoxymethyl group.

[0237] 1 H NMR(400MHz,CDCl3,δ in ppm)7.44(d,J=1.7Hz,4H),7.37(d,J=1.7Hz,2H),7.27(d,J=2.4Hz,2H),7.23(br,4H),7.15(d,J=2.2Hz,2H), 4.44(s,4H),3.88-3.81(m,2H),2.72(s,6H),2.39(s,6H),2.37(s,6H),1.37(s,36H),0.81(d,J=5.6Hz,12H).

[0238] [ka]

[0239] [Synthesis Example 10] A thoroughly dried 200 mL three-neck flask was charged with 3.22 g (0.0033 mol) of compound (9), 30 mL of methanol, and 30 mL of THF, and the atmosphere was replaced with nitrogen. 5 mL of a 4 M hydrogen chloride dioxane solution was added, and the mixture was stirred at room temperature for 40 hours. After the reaction, the mixture was quenched with saturated aqueous sodium bicarbonate, extracted three times with methylene chloride, and the resulting organic layer was dried over sodium sulfate. The white solid obtained by concentration on a rotary evaporator was purified on a silica gel column (hexane:methylene chloride = 1:1) to give 1.94 g of compound (10) (white powder, 66% yield).

[0240] 1 H NMR(400MHz,CDCl3,δ in ppm)7.42(d,J=1.7Hz,4H),7.35(dd,J=1.7,1.7Hz,2H),7.24(d,J=1.8Hz,2H),7.20(br,2H),7.16(dd,J =2.2,8.4Hz,4H),3.77-3.67(m,2H),2.43(s,6H),2.39(s,6H),1.30(s,36H),0.84(s,6H),0.62(s,6H).

[0241] [ka]

[0242] Example 1A All manipulations were performed in a glove box. 65.6 mg (0.28 mmol) of zirconium(IV) chloride and 30 mL of toluene were added to a thoroughly dried 50 mL vial and cooled to -40 °C. Similarly, 300.0 mg (0.28 mmol) of compound (8) and 20 mL of toluene were added to a thoroughly dried 30 mL vial and cooled to -40 °C. The 50 mL vial was removed from the freezer and 0.38 mL (1.13 mmol) of 3 M methylmagnesium bromide in diethyl ether was quickly added and stirred until the mixture turned yellow (approximately 5 min). After confirming the color change, the 30 mL vial was removed from the freezer and transferred to the 50 mL vial. The mixture was slowly warmed to room temperature and stirred for 5 hours. After the reaction, the mixture was filtered through a syringe filter, concentrated on a rotary evaporator, dissolved in toluene, and filtered again through a syringe filter. The mixture was concentrated again using a rotary evaporator, hexane was added thereto, and the mixture was cooled overnight. The precipitated solid was filtered off to obtain 148.0 mg of compound (A) (white powder, yield 45%).

[0243] 1 H NMR(400MHz,C6D6,δ in ppm)8.20(dd,J=0.7,2.0Hz,2H),8.11(dd,J=0.7,2.0Hz,2H),7.48-7.42(m,4H),7.34-7.28(m,8H),7.18(dd,J=0.7,2.7Hz,2H),7.01(dd,J=0.7, 2.7Hz,2H),3.61-3.51(m,2H),2.25(s,6H),2.23(s,6H),1.67(s,18H),1 .42(s,18H),0.79(d,J=6.8Hz,6H),0.65(d,J=6.1Hz,6H),-1.20(s,6H).

[0244] [ka]

[0245] Example 2A All manipulations were performed in a glove box. 60.1 mg (0.19 mmol) of hafnium(IV) chloride and 35 mL of toluene were added to a thoroughly dried 50 mL vial and cooled to -40 °C. Similarly, 200.0 mg (0.19 mmol) of compound (8) and 14 mL of toluene were added to a thoroughly dried 30 mL vial and cooled to -40 °C. The 50 mL vial was removed from the freezer, and 0.25 mL (0.75 mmol) of 3 M methylmagnesium bromide in diethyl ether was quickly added and stirred for 10 minutes. The 30 mL vial was then removed from the freezer and transferred to the 50 mL vial. The mixture was allowed to warm to room temperature and stirred for 2.5 hours. After the reaction, the mixture was filtered through a syringe filter, concentrated on a rotary evaporator, dissolved in toluene, and filtered again through a syringe filter. The solution was concentrated again using a rotary evaporator, dissolved in benzene, and filtered again using a syringe filter. The resulting solution was evaporated to dryness using a rotary evaporator to obtain 128.6 mg of compound (B) (light gray powder, 54% yield).

[0246] 1 H NMR(400MHz,C6D6,δ in ppm)8.22(dd,J=0.7,1.7Hz,2H),8.12(dd,J=0.5,2.0Hz,2H),7.48-7.42(m,4H),7.35(dd,J =0.6,2.3Hz,2H),7.32(dd,J=2.0,8.8Hz,2H),7.29(dd,J=0.7,2.1Hz,2H),7.24(dd,J=0.6,8 .7Hz,2H),7.17(m,2H),7.01(dd,J=0.7,2.3Hz,2H),3.68-3.60(m,2H),2.27(s,6H),2.23(s, 6H),1.69(s,18H),1.43(s,18H),0.76(d,J=6.8Hz,6H),0.67(d,J=6.1Hz,6H),-1.50(s,6H).

[0247] [ka]

[0248] [Comparative Example 1A] All manipulations were performed in a glove box. A thoroughly dried 100 mL vial was charged with 52.5 mg (0.23 mmol) of zirconium(IV) chloride and 30 mL of toluene and cooled to -40 °C. Similarly, a thoroughly dried 30 mL vial was charged with 200.0 mg (0.23 mmol) of compound (10) and 20 mL of toluene and cooled to -40 °C. The 50 mL vial was removed from the freezer and immediately added with 0.30 mL (0.90 mmol) of 3 M methylmagnesium bromide in diethyl ether. The mixture was stirred for approximately 5 min until the color changed to yellow. After confirming the color change, the 30 mL vial was removed from the freezer and transferred to a 100 mL vial. The mixture was allowed to slowly warm to room temperature and stirred for 5 h. After the reaction, the mixture was filtered through a syringe filter and concentrated using a rotary evaporator. Hexane was added to the mixture, and the mixture was cooled overnight. The precipitated solid was filtered off to obtain 143.6 mg of compound (C) (white powder, 63% yield).

[0249] 1 H NMR(400MHz,C6D6,δ in ppm)7.65(d,J=1.7Hz,4H),7.48(dd,J=2.0,2.0Hz,2H),7.37(dd,J=0.7,2.4Hz,2H),7.28(dd,J=0.7,2.2Hz,2H),7.14(dd,J=0.8,2.3Hz,2H),6. 99(dd,J=0.7,2.4Hz,2H),3.70-3.60(m,2H),2.37(s,6H),2.19(s,6H), 1.41(s,36H),0.81(d,J=6.6Hz,6H),0.73(d,J=6.3Hz,6H),0.04(s,6H).

[0250] [ka]

[0251] [Comparative example 2A] In a thoroughly dried 100 mL Schlenk tube, 0.074 g (0.23 mmol) of hafnium(IV) chloride and 30 mL of dehydrated toluene were added under a nitrogen atmosphere and stirred at -78 °C. 0.33 mL (1.00 mmol) of 4.5 equivalents of MeMgBr (3 M ether solution) was added in small portions and stirred at -45 °C for 1 hour. In a separate thoroughly dried 100 mL Schlenk tube, 0.200 g (0.23 mmol) of compound (10) and 15 mL of toluene were added under a nitrogen atmosphere and stirred at -78 °C. The resulting mixture was then added dropwise to the reaction solution via cannulation. The reaction solution was stirred overnight while slowly warming from -78 °C to room temperature. After the reaction, the solution was concentrated using a vacuum pump and brought into a glove box. Toluene was added to the concentrated solid, stirred thoroughly, and filtered through a 1.0 μm filter to remove insoluble matter. The filtrate was concentrated using a rotary evaporator, and hexane / toluene was added. The mixture was then placed in a freezer (-40°C) for recrystallization to obtain 0.138 g of compound (D) (white solid, 55% yield). 1 This was done by measuring the H-NMR spectrum.

[0252] 1 H-NMR(400MHz,tol-d8,δ in ppm)7.53-7.00(14H),3.68(m,2H),2.38(s,6H),2.21(s,6H),1.40(s,36H),0.81(d,6H),0.69(d,6H),-0.33(s,6H).

[0253] [ka]

[0254] [Synthesis Example 11] A thoroughly dried 300 mL three-neck flask was charged with 5.50 g (0.015 mol) of 3,3'-dibromo-5,5'-dimethyl-[1,1'-biphenyl]-2,2'-diol, 6.12 g (0.044 mol) of potassium carbonate, and 120 mL of acetone under a nitrogen atmosphere and stirred at room temperature for 30 minutes. 3.5 mL (0.037 mol) of dimethyl sulfate was added and stirred overnight at room temperature. The reaction was quenched with 50 mL of water, and after distilling off the acetone, 100 mL of ethyl acetate was added and extracted with ethyl acetate. The organic layer was washed with brine (saturated aqueous sodium chloride solution) and dried over sodium sulfate. The dried solution was concentrated using a rotary evaporator and purified using a silica gel column (hexane:ethyl acetate = 20:1) to obtain 5.559 g of compound (11) (white powder, 94% yield).

[0255] 1 H NMR(400MHz,CDCl3,δ in ppm)7.00(s,1H),7.33(s,1H),3.48(s,6H),2.25(s,6H).

[0256] [ka]

[0257] [Synthesis Example 12] A thoroughly dried 300 mL three-neck flask was charged with 5.570 g (0.013 mol) of compound (6) and 50 mL of deoxygenated tetrahydrofuran under a nitrogen atmosphere and then transferred to a dry ice / methanol bath for cooling. 8.51 mL (0.014 mol) of a 1.6 M n-butyllithium hexane solution was slowly added dropwise, and the flask was then transferred to an ice bath and reacted for 1.5 hours. After the reaction, the flask was again transferred to a dry ice / methanol bath and cooled to -78 °C. 152 mL (0.014 mol) of trimethoxyborane was quickly added, and the flask was then transferred to an ice bath and reacted for 1.5 hours. Then, under a nitrogen atmosphere, 2.33 g (0.0058 mol) of compound (11), 5.50 g (0.0259 mol) of tripotassium phosphate, 0.029 g (0.13 mmol) of palladium(II) acetate, 0.106 g (0.26 mmol) of Sphos, and 75 mL of THF were added to a reaction vessel and stirred. 25 mL of water was added dropwise while monitoring the internal temperature. After the temperature had subsided, the mixture was heated to 80 °C and stirred for an additional 18 hours. After the reaction, the mixture was extracted three times with ethyl acetate, and the resulting organic layer was dried over sodium sulfate. The crude product obtained by concentration on a rotary evaporator was purified on a silica gel column (hexane:ethyl acetate = 20:1) to obtain 4.634 g of compound (12) (white powder, 72% yield).

[0258] 1 H NMR(400MHz,CDCl3,δ in ppm)8.11(s,4H),7.46-7.44(d,J=8.4Hz,4H),7.35(s,2H),7.29-7.23(m,10H ),4.25(s,4H),3.49(s,6H)2.48(s,6H),2.40(d,J=3.6Hz,12H),1.45(s,36H).

[0259] [ka]

[0260] [Synthesis Example 13] In a thoroughly dried 300 mL three-neck flask, 4.50 g (0.0041 mol) of compound (12), 120 mL of dichloromethane, and 90 mL of 4 M hydrogen chloride in dioxane were added under a nitrogen atmosphere and stirred at room temperature for 15 hours. After the reaction, the mixture was quenched with saturated aqueous sodium bicarbonate and extracted with methylene chloride. The resulting organic layer was dried over sodium sulfate. The white solid obtained by concentration on a rotary evaporator was purified on a silica gel column (hexane:ethyl acetate = 20:1) to give 2.736 g of compound (13) (white powder, 66% yield).

[0261] 1 H NMR(400MHz,CDCl3,δ in ppm)8.12(s,4H),7.40(d,J=8.4Hz,4H),7.32(s,2H),7.29(s,2H),7.22(s, 2H),7.13(t,J=10.4,8.8Hz,6H),3.42(s,6H),2.40(s,12H),1.44(s,36H).

[0262] [ka]

[0263] [Comparative example 3A] All manipulations were performed in a glove box. A thoroughly dried 50 mL vial was charged with 45 mg (0.20 mmol) of zirconium(IV) chloride and 32 mL of toluene and cooled to -40 °C. Similarly, a thoroughly dried 30 mL vial was charged with 202 mg (0.20 mmol) of compound (13) and 8 mL of toluene and cooled to -40 °C. The 50 mL vial was removed from the freezer and 0.30 mL (0.90 mmol) of 3 M methylmagnesium bromide in diethyl ether was quickly added. The mixture was stirred until the color changed (approximately 2 min). After confirming the color change, the 30 mL vial was removed from the freezer and transferred to the 50 mL vial. The mixture was allowed to slowly warm to room temperature and stirred for 4 h. After the reaction, the mixture was filtered through a syringe filter and concentrated using a rotary evaporator. Hexane was added thereto and the mixture was cooled overnight. The precipitated solid was filtered off to obtain 79 mg of compound (E) (white powder, yield 35%).

[0264] 1 H NMR(400MHz,C6D6,δ in ppm)8.26(s,2H),8.15(s,2H),7.44(s,4H),7.39-7.27(m,9H),6.89(s,2H),2 .66(s,6H),2.24(d,J=6.8Hz,12H),1.71(s,18H),1.47(s,18H),-1.16(s,6H).

[0265] [ka]

[0266] [Synthesis Example 14] A thoroughly dried 100 mL three-neck flask was charged with 2.02 g (4.42 mmol) of compound (4) and 30 mL of deoxygenated tetrahydrofuran under a nitrogen atmosphere and cooled to -78 °C in a dry ice bath. 2.90 mL (4.64 mmol) of a 1.59 M n-butyllithium hexane solution was slowly added, and the mixture was allowed to react for 0.5 hours. 0.62 mL (5.53 mmol) of trimethoxyborane was added, and the mixture was allowed to react at room temperature for 1 hour. The mixture was transferred to an ice bath, and 1.86 mL (32.5 mmol) of acetic acid was added and stirred for 10 minutes. 30% hydrogen peroxide was then slowly added and stirred for 3 hours. After the reaction, the mixture was extracted three times with ethyl acetate. The resulting organic layer was washed with saturated aqueous sodium bicarbonate, saturated aqueous ammonium chloride, and saturated brine, and then dried over sodium sulfate. The mixture was concentrated using a rotary evaporator to obtain a colorless oil, which was purified using a silica gel column (hexane:ethyl acetate=9:1) to obtain 1.46 g of compound (14) (yellow oil, 84% yield).

[0267] 1 H NMR(400MHz,CDCl3,δ in ppm)7.36(dd,J=2.2,0.7Hz,1H),7.19(dd,J=2.2,0.5Hz,1H),6.79(dd,J=2.2,0.7Hz,1H),6.77(dd,J=2.0,0.5Hz,1H),5 .86(s,1H),3.93-3.84(m,1H),3.73-3.64(m,1H),2.31(s,3H),2.28(s,3H),1.06(d,J=3.0Hz,6H),1.05(d,J=2.0Hz,6H).

[0268] [ka]

[0269] [Synthesis Example 15] A thoroughly dried 100 mL three-neck flask was charged with 6.12 g (0.05 mol) of 2,4-dimethylphenol and 30 mL of deoxygenated tetrahydrofuran under a nitrogen atmosphere and then cooled in an ice bath. 7.52 mL (0.10 mol) of N,N-diisopropylethylamine was added. 17.0 mL (0.10 mol) of chloromethyl methyl ether was then added dropwise and the mixture was allowed to react at room temperature overnight. After the reaction, the mixture was extracted three times with ethyl acetate. The resulting organic layer was washed with saturated aqueous sodium bicarbonate, saturated aqueous ammonium chloride, and saturated brine, and then dried over sodium sulfate. The resulting colorless oil obtained by concentration on a rotary evaporator was purified on a silica gel column (hexane:ethyl acetate = 19:1) to give 5.80 g of compound (15) (clear oil, 70% yield). MOM in compound (15) means a methoxymethyl group.

[0270] 1 H NMR(400MHz,CDCl3,δ in ppm)6.94(dd,J=1.6,0.4Hz,1H),6.92(d,J=0.8Hz,1H),6.91(s,1H),5.14(s,2H),3.45(s,3H),2.24(s,3H),2.21(s,3H).

[0271] [ka]

[0272] [Synthesis Example 16] A thoroughly dried 100 mL three-neck flask was charged with 0.57 g (3.45 mmol) of compound (15) and 10 mL of deoxygenated tetrahydrofuran under a nitrogen atmosphere and then cooled in an ice bath. 2.26 mL (3.61 mmol) of a 1.59 M n-butyllithium hexane solution was slowly added, and the mixture was allowed to react for 2 hours. 0.40 mL (5.53 mmol) of trimethoxyborane was added, and the mixture was allowed to react for 1.5 hours. Under a nitrogen atmosphere, 1.35 g (3.43 mmol) of compound (14), 1.19 g (8.62 mmol) of potassium carbonate, 40.4 mg (0.03 mmol) of tetrakis(triphenylphosphine)palladium (zerovalent), and 40 mL of THF were added to the reaction vessel and stirred. 10 mL of water, which had been previously bubbled with nitrogen, was added dropwise while monitoring the internal temperature. After the temperature had subsided, the mixture was heated to 70 °C and stirred for an additional 18 hours. After the reaction, the mixture was extracted three times with ethyl acetate. The resulting organic layer was washed with saturated aqueous sodium bicarbonate, saturated aqueous ammonium, and saturated brine, and then dried over sodium sulfate. The colorless oil obtained by concentration on a rotary evaporator was purified on a silica gel column (hexane:ethyl acetate = 9:1) to give 1.06 g of compound (16) (white crystals, 64% yield).

[0273] 1 H NMR (400 MHz, CDCl3, δ in ppm)7.23(d,J=0.7Hz,1H),7.17(s,1H),7.08(s,1H),6.98(d,J=1.7Hz,1H),6. 84(d,J=0.5Hz,1H),6.75(dd,J=2.2,0.7Hz,1H),5.92(dd,J=2.7,0.2Hz,1H),4. 73(s,2H),3.89-3.80(m,1H),3.68-3.59(m,1H),3.21(s,3H),2.35(s,3H),2.34 (s,3H),2.30(s,3H),2.90(s,3H),1.10(d,J=6.1Hz,6H),0.68(d,J=4.9Hz,6H).

[0274] [ka]

[0275] [Synthesis Example 17] A thoroughly dried 100 mL three-neck flask was charged with 1.06 g (2.21 mmol) of compound (16) and 30 mL of ultra-dehydrated dichloromethane under a nitrogen atmosphere and cooled to -40 °C in a dry ice bath. 1.13 mL (6.64 mmol) of N,N-diisopropylethylamine was added. After the addition, 0.54 mL (3.32 mmol) of trifluoromethanesulfonic anhydride was added dropwise and stirred for 0.5 hours. After the reaction, the mixture was extracted three times with dichloromethane. The resulting organic layer was washed with saturated aqueous sodium bicarbonate and saturated brine, then dried over sodium sulfate. The mixture was concentrated using a rotary evaporator to give 1.33 g of compound (17) (white crystals, 92% yield). Tf in compound (17) means a trifluoromethanesulfonyl group.

[0276] 1 H NMR(400MHz,CDCl3,δ in ppm)7.33(dd,J=2.2,0.7Hz,1H),7.25(dd,J=2.4,0.7Hz,1H),7.17(dd,J=2.4,0.7Hz,1H),7.01(d,J=2.2Hz,1H),6.99(ddd,J=1.5,1.5,0.7Hz,2H), 4.71(s,2H),3.98-3.88(m,1H),3.65-3.56(m,1H),3.18(s,3H),2.36(s,3 H),2.34(s,6H),2.31(s,3H),1.10(d,J=6.4Hz,6H),0.66(d,J=5.8Hz,6H).

[0277] [ka]

[0278] [Synthesis Example 18] A thoroughly dried 500 mL three-neck flask was charged with 1.23 g (2.85 mmol) of compound (6) and 20 mL of deoxygenated tetrahydrofuran under a nitrogen atmosphere and then cooled in an ice bath. 1.76 mL (2.82 mmol) of a 1.59 M n-butyllithium hexane solution was slowly added, and the mixture was allowed to react for 2 hours. 0.28 mL (2.47 mmol) of trimethoxyborane was added, and the mixture was allowed to react for 1.5 hours. Under a nitrogen atmosphere, 1.32 g (2.16 mmol) of compound (17), 1.92 g (5.90 mmol) of cesium carbonate, 0.31 g (2.56 mmol) of potassium bromide, 18.6 mg (0.08 mmol) of palladium(II) acetate, 69.2 mg (0.17 mmol) of SPhos, and 80 mL of THF were added to the reaction vessel and stirred. 10 mL of water, which had been previously bubbled with nitrogen, was added dropwise while monitoring the internal temperature. After the temperature had subsided, the mixture was heated to 70 °C and stirred for an additional 18 hours. After the reaction, the mixture was extracted three times with ethyl acetate. The resulting organic layer was washed with saturated aqueous sodium bicarbonate, saturated aqueous ammonium, and saturated brine, and then dried over sodium sulfate. The colorless oil obtained by concentration on a rotary evaporator was purified on a silica gel column (hexane:ethyl acetate = 19:1) to give 1.62 g of compound (18) (white crystals, 84% yield).

[0279] 1H NMR(400MHz,CDCl3,δ in ppm)8.12(d,J=2.0Hz,2H),7.47(dd,J=8.5,1.7Hz,2H),7.39(d,J=1.7Hz,1H),7.36(d,J=2.0Hz,1H),7.33( d,J=1.7Hz,1H),7.31(s,1H),7.29(s,1H),7.25(d,J=1.7Hz,1H),7.19(d,J=2.2Hz,1H),7.14(s,1H),7.08( s,1H),6.99(s,1H),4.76(s,2H),4.29(s,2H),3.88-3.82(m,1H),3.75-3.69(m,1H),3.25(s,3H),2.47(s,3 H),2.39(s,3H),2.38(s,3H),2.36(s,6H),2.32(s,3H),1.47(s,18H),0.87(d,J=7.3Hz,6H),0.72(br,6H).

[0280] [ka]

[0281] [Synthesis Example 19] A thoroughly dried 100 mL two-neck flask was charged with 1.60 g (1.79 mmol) of compound (18), 25 mL of dichloromethane, and 25 mL of methanol under a nitrogen atmosphere and then transferred to an ice bath for cooling. 15 mL of concentrated hydrochloric acid was added and the mixture was stirred at room temperature overnight. After the reaction, the mixture was extracted three times with dichloromethane. The resulting organic layer was washed with saturated aqueous sodium bicarbonate and saturated brine, and then dried over sodium sulfate. The colorless oil obtained by concentration using a rotary evaporator was purified using a silica gel column (hexane:dichloromethane = 7:3) to obtain 0.38 g of compound (19) (white crystals, 26% yield).

[0282] 1H NMR(400MHz,CDCl3,δ in ppm)8.16(d,J=1.5Hz,2H),7.42(d,J=7.6Hz,3H),7.34(br,2H),7.24(br,3H),7.18(br,3H),7.16(br,1H),6.96(br,1H),6.94(br,1H),3. 82-3.76(m,1H),3.61(br,1H),2.46(s,3H),2.40(s,3H),2.39(s,3H),2.28(s,3H),2.23(s,3H),1.47(s,18H),0.83(br,6H),0.64(br,6H).

[0283] [ka]

[0284] [Comparative example 4A] All manipulations were performed in a glove box. 58.3 mg (0.25 mmol) of zirconium(IV) chloride and 30 mL of toluene were added to a thoroughly dried 50 mL vial and cooled to -40 °C. Similarly, 200.0 mg (0.25 mmol) of compound (19) and 10 mL of toluene were added to a thoroughly dried 30 mL vial and cooled to -40 °C. The 50 mL vial was removed and 0.33 mL (0.99 mmol) of 3 M methylmagnesium bromide in diethyl ether was quickly added and stirred until the mixture turned yellow. After confirming the color change, the 30 mL vial was removed and transferred to a 50 mL vial and stirred at room temperature for 4 hours. After the reaction, the mixture was filtered, concentrated on a rotary evaporator, and extracted with hexane. The mixture was again dried on a rotary evaporator to obtain 87.3 mg of compound (F) (white solid, 38% yield).

[0285] 11H NMR (400 MHz, C6D6, δ in ppm): 8.46 (dd, J = 2.7, 1.2 Hz, 2H), 7.80 (d, J = 8.5 Hz, 1H), 7.66 (d, J = 7.1 Hz, 1H), 7.65 (s, 1H), 7.55 (dd, J = 8.8, 2.0 Hz, 1H), 7.46 (dd, J = 2.4, 0.7 Hz, 1H), 7.38 (dd, J = 2.4, 0.7 Hz, 1H), 7.25 (dd, J = 2.2, 0.5 Hz, 1H), 7.09 (d, J = 2.2 Hz, 1H), 7.08 (dd, J = 2.2, 0.7 Hz, 1H), 7.01 (dd, J = 2.2, 0.5 Hz, 1H), 6.93 (dd, J = 2.5, 0.5 Hz, 1H), 6.89 (dd, J = 1.7, 0.7 Hz, 1H), 3.63 - 3.53 (m, 2H), 2.33 (s, 3H), 2.26 (s, 6H), 2.23 (s, 3H), 2.14 (s, 3H), 1.48 (s, 9H), 1.46 (s, 9H), 0.77 (d, J = 6.6 Hz, 3H), 0.72 (d, J = 6.1 Hz, 3H), 0.62 (d, J = 6.3 Hz, 3H), 0.56 (d, J = 6.6 Hz, 3H), 0.16 (s, 3H), -0.11 (s, 3H).

[0286] [Chemical formula]

[0287] [Comparative Example 5A] All manipulations were performed in a glove box. A thoroughly dried 50 mL vial was charged with 80.8 mg (0.25 mmol) of hafnium(IV) chloride and 30 mL of toluene and cooled to -40 °C. Similarly, a thoroughly dried 30 mL vial was charged with 202.0 mg (0.25 mmol) of compound (19) and 10 mL of toluene and cooled to -40 °C. The 50 mL vial was removed and 0.33 mL (0.99 mmol) of 3 M methylmagnesium bromide in diethyl ether was quickly added and stirred until the mixture turned yellow. After confirming the color change, the 30 mL vial was removed and transferred to a 50 mL vial and stirred at room temperature for 4 hours. After the reaction, the mixture was filtered, concentrated on a rotary evaporator, and extracted with hexane. The mixture was again dried on a rotary evaporator to obtain 157.1 mg of compound (G) (white solid, 62% yield).

[0288] 1 H NMR(400MHz,C6D6,δ in ppm)8.48(dd,J=2.0,0.5Hz,1H),8.47(dd,J=2.0,0.5Hz,1H),7.84(d,J=8.5Hz,1H),7.65(dd,J=8.8,2.0Hz,1H),7.61(dd,J=8.8,0.7Hz,1H),7.54(dd, J=8.5,1.7Hz,1H),7.48(dd,J=2.4,0.7Hz,1H),7.37(dd,J=2.4,0.7Hz,1H) ,7.23(dd,J=2.2,0.5Hz,1H),7.09(d,J=2.2Hz,1H),7.06(dd,J=2.4,0.7Hz, 1H),7.01(dd,J=2.5,0.8Hz,1H),6.93(dd,J=2.2,0.5Hz,1H),6.90(dd,J=1 .5,0.5Hz,1H),3.72-3.63(m,2H),2.33(s,3H),2.27(s,3H),2.26(s,3H),2. 19(s,3H),2.13(s,3H),1.48(s,9H),1.46(s,9H),0.84(d,J=6.6Hz,3H),0. 74(d,J=6.3Hz,3H),0.64(dd,J=6.1,4.3Hz,6H),0.00(s,3H),-0.39(s,3H).

[0289] [ka]

[0290] <Production of ethylene polymer> Example 1B A 500 mL glass reactor, thoroughly purged with nitrogen, was charged with 250 mL of toluene, and ethylene was passed through at 100 L / hr to saturate the liquid and gas phases. Polymerization was then initiated by adding 0.2 mmol (calculated as aluminum atom) of triisobutylaluminum, 0.005 μmol of compound (A), and 0.02 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate. Ethylene was continuously supplied at 100 L / hr, and polymerization was carried out for 5 minutes at an internal temperature of 25°C under atmospheric pressure. The polymerization was then terminated by the addition of a small amount of methanol. After polymerization, the reactant was added to 750 mL of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 80°C for 10 hours, yielding 2.07 g of ethylene polymer. The polymerization results are shown in Table 1.

[0291] Example 2B The polymerization results are shown in Table 1.

[0292] [Comparative example 1B] The polymerization was carried out in the same manner as in Example 1B, except that the compound (C) was used instead of the compound (A) as the catalyst precursor, to obtain 0.62 g of an ethylene polymer. The polymerization results are shown in Table 1.

[0293] [Comparative Example 2B] A 500 mL glass reactor, thoroughly purged with nitrogen, was charged with 250 mL of toluene, and ethylene was passed through at 100 L / hr to saturate the liquid and gas phases. Polymerization was then initiated by adding 0.2 mmol (calculated as aluminum atom) of triisobutylaluminum, 0.050 μmol of compound (D), and 0.20 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate. Ethylene was continuously supplied at 100 L / hr, and polymerization was carried out for 5 minutes at an internal temperature of 25°C under atmospheric pressure. The polymerization was then terminated by the addition of a small amount of methanol. After polymerization was complete, the reaction mixture was added to 750 mL of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 80°C for 10 hours, yielding 0.69 g of ethylene polymer. The polymerization results are shown in Table 1.

[0294] [Comparative example 3B] A 500 mL glass reactor, thoroughly purged with nitrogen, was charged with 250 mL of toluene, and ethylene was passed through at 100 L / hr to saturate the liquid and gas phases. Polymerization was then initiated by adding 0.2 mmol (calculated as aluminum atom) of triisobutylaluminum, 0.010 μmol of compound (F), and 0.04 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate. Ethylene was continuously supplied at 100 L / hr, and polymerization was carried out for 5 minutes at an internal temperature of 25°C under atmospheric pressure. The polymerization was then terminated by the addition of a small amount of methanol. After polymerization was complete, the reactant was added to 750 mL of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 80°C for 10 hours, yielding 0.54 g of ethylene polymer. The polymerization results are shown in Table 1.

[0295] [Comparative example 4B] A 500 mL glass reactor, thoroughly purged with nitrogen, was charged with 250 mL of toluene, and ethylene was passed through at 100 L / hr to saturate the liquid and gas phases. Polymerization was then initiated by adding 0.2 mmol (calculated as aluminum atom) of triisobutylaluminum, 1.000 μmol of compound (G), and 4.00 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate. Ethylene was continuously supplied at 100 L / hr, and polymerization was carried out for 5 minutes at an internal temperature of 25°C under atmospheric pressure. The polymerization was then terminated by the addition of a small amount of methanol. After polymerization was complete, the reactant was added to 750 mL of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 80°C for 10 hours, yielding 1.04 g of ethylene polymer. The polymerization results are shown in Table 1.

[0296] [Table 1]

[0297] In Table 1 and Table 2 described later, TIBA represents triisobutylaluminum, and TrB represents triphenylcarbenium tetrakis(pentafluorophenyl)borate.

[0298] Example 3B Triisobutylaluminum (0.01 mmol, calculated as aluminum atoms) was injected into each injection port of a parallel polymerization apparatus (Endeavor) using a dedicated syringe, followed by 3.3 mL of dehydrated toluene. The temperature inside the polymerization vessel was raised to 50°C, and ethylene was introduced at 7 bar (gauge pressure). Then, 0.02 μmol of compound (A) was injected into each injection port, followed by 0.08 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate. Finally, 0.7 mL of toluene for washing was injected to initiate polymerization. After 30 minutes, 0.2 mL of isobutyl alcohol was added to terminate the polymerization. After cooling to room temperature and depressurizing, the polymerization vessel was opened and the polymerization solution was removed. The polymerization solution was added to methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the mixture was dried under reduced pressure at 80°C for 10 hours. The ethylene absorption was 3.69 mmol, and 0.103 g of ethylene polymer was obtained. The polymerization results are shown in Table 2. The amount of ethylene absorbed refers to the amount of ethylene monomer polymerized by the transition metal compound [A] during the polymerization of ethylene.

[0299] [Comparative Example 5B] Polymerization was carried out in the same manner as in Example 3B, except that compound (C) was used instead of compound (A) as the catalyst precursor. The ethylene absorption amount was 2.61 mmol, and 0.073 g of ethylene polymer was obtained. The polymerization results are shown in Table 2.

[0300] [Comparative Example 6B] Polymerization was carried out in the same manner as in Example 3B, except that compound (E) was used instead of compound (A) as the catalyst precursor. The amount of ethylene absorbed was 2.27 mmol, and 0.064 g of ethylene polymer was obtained. The polymerization results are shown in Table 2.

[0301] [Table 2]

Claims

1. A transition metal compound [A] represented by the following general formula (I): 【Chemistry 1】 (In the general formula (I), R １ ~R ９ and R １２ ~R １４ each independently represents a hydrogen atom, a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen atom, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group; The R １ ~R ９ and R １２ ~R １４ Adjacent substituents among the above may be bonded to each other to form a ring, R １０ and R １１ each independently represents a fused polycyclic hydrocarbon group or a fused heterocyclic compound group, and the fused polycyclic hydrocarbon group and the fused heterocyclic compound group may further have a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen atom, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group as a substituent; D １ and D ２ are each independently -OR １５ , -SR １５ , -NR １６ R １７ , or -PR １６ R １７ (The solid lines indicate bonds with adjacent atoms. R １５ is a hydrocarbon group having two or more carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group; R １６ and R １７ are each independently a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group; L １ and L ２ are each independently an oxygen atom, a sulfur atom, 【Chemistry 2】 (The solid lines indicate bonds with adjacent atoms. R １８ is a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen atom, a halogen-containing hydrocarbon group, a boron-containing group, a phosphorus-containing group, a germanium-containing group, or a tin-containing group; M is a transition metal atom of Group 4 of the periodic table; Two Xs each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a halogen-containing hydrocarbon group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a germanium-containing group, a tin-containing group, or a diene-based divalent derivative group, and two Xs may be bonded to each other to form a ring.

2. The R １０ and R １１ and each independently represent a fused polycyclic hydrocarbon group or a fused heterocyclic compound group which may have a hydrocarbon group as a substituent.

3. The above D １ and D ２ are each independently -OR １５ and R １５ is a residue of a hydrocarbon group having 2 to 20 carbon atoms other than an aryl group, an aryl group having 7 to 25 carbon atoms, a silicon-containing group, a halogen-containing hydrocarbon group, or a heterocyclic compound containing an oxygen atom, a sulfur atom, or a nitrogen atom.

4. The R １５ is a linear or branched alkyl group having 3 to 15 carbon atoms or a cyclic saturated hydrocarbon group having 3 to 15 carbon atoms.

5. Said L １ and L ２ The transition metal compound [A] according to claim 1, wherein is an oxygen atom.

6. The transition metal compound [A] according to claim 1, wherein M is a zirconium atom or a hafnium atom.

7. An olefin polymerization catalyst comprising the transition metal compound [A] according to any one of claims 1 to 6.

8. an organometallic compound [B-1], and The olefin polymerization catalyst according to claim 7, further comprising at least one compound [B] selected from the group consisting of compounds [B-2] that react with the transition metal compound [A] to form an ion pair.

9. The olefin polymerization catalyst according to claim 7, further comprising a support, wherein the transition metal compound [A] is supported on the support.

10. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 7.

11. The method for producing an olefin polymer according to claim 10, wherein the olefin is at least one selected from the group consisting of α-olefins having 2 to 30 carbon atoms, cyclic olefins, and non-conjugated diolefins.

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