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 which can be used for producing an olefin polymer having a high molecular weight, a catalyst for olefin polymerization, and a method for producing an olefin polymer.SOLUTION: The transition metal compound [A] is represented by general formula (I) (wherein M is a Hf atom).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] The transition metal compound described in Patent Document 1 leaves room for improvement in terms of the molecular weight of the resulting olefin polymer. Therefore, an object of the present invention is to provide a transition metal compound that can be used in the production of a high-molecular-weight olefin polymer, an olefin polymerization catalyst, and a method for producing an olefin polymer. [Means for solving the problem]

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

[12] . [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 are each independently 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; 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 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 hafnium atom, 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 hydrocarbon group.

[0012] [3] The above D 1 and D 2 are each independently, -OR 15 and R 15 is a hydrocarbon group having 2 to 20 carbon atoms, a silicon-containing group, or a halogen-containing hydrocarbon group.

[0013] [4] R 15 is a hydrocarbon group having 3 to 20 carbon atoms.

[0014] [5] R 15 is a linear or branched alkyl group having 3 to 20 carbon atoms.

[0015] [6] R 15 is a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms.

[0016] [7] Said L 1 and L 2 The transition metal compound [A] according to any one of [1] to [6], wherein is an oxygen atom.

[0017] [8] An olefin polymerization catalyst comprising the transition metal compound [A] according to any one of [1] to [7].

[0018] [9] Organometallic compound [B-1], Organoaluminum oxy compounds [B-2], and The olefin polymerization catalyst according to [8], further comprising at least one compound [B] selected from the group consisting of compounds [B-3] that react with the transition metal compound [A] to form an ion pair.

[0019]

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

[0020]

[11] A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of [8] to

[10] .

[0021]

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

[11] , 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]

[0022] According to the transition metal compound of the present invention, the olefin polymerization catalyst containing the transition metal compound, and the process for producing an olefin polymer, it is possible to polymerize an olefin polymer having a high molecular weight. [Brief explanation of the drawings]

[0023] [Figure 1] FIG. 1 shows the measurement conditions and results of the annealing measurement by a differential scanning calorimeter for the ethylene polymer obtained in Example 15. [Figure 2]FIG. 2 shows the measurement conditions and results of the annealing measurement by a differential scanning calorimeter for the ethylene polymer obtained in Example 9. DETAILED DESCRIPTION OF THE INVENTION

[0024] 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.

[0025] <Transition metal compound [A]> The transition metal compound [A] according to the present invention is represented by the following general formula (I).

[0026] [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.

[0027] 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.

[0028] 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.

[0029] The silicon-containing group preferably has 0 to 30 carbon atoms, and more preferably 0 to 20 carbon atoms.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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 ka ... Examples include rubazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenarsazinyl, isothiazolyl, perimidinyl, phenothiazinyl, phenoxazinyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidyl, piperazinyl, indolinyl, isoindolinyl, quinuclidinyl, triazinyl, and phenanthrolinyl groups.

[0040] 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.

[0041] The halogen atoms include fluorine, chlorine, bromine, and iodine.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] In the general formula (I), R 10 and R 11are each independently 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 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] R 10 and R 11 is preferably a hydrocarbon group, a nitrogen-containing group, or an oxygen-containing group, more preferably a hydrocarbon group, even more preferably an aryl group having 6 to 30 carbon atoms, an alkyl-substituted aryl group having 7 to 30 carbon atoms, or a nitrogen-containing group having 6 to 30 carbon atoms, still more preferably an aryl group having 6 to 20 carbon atoms, an alkyl-substituted aryl group having 7 to 20 carbon atoms, or a nitrogen-containing group having 6 to 20 carbon atoms, and particularly preferably an alkyl-substituted aryl group having 7 to 15 carbon atoms (for example, a 3,5-di-tert-butylphenyl group).

[0049] 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.

[0050] R 15is 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 14 Examples 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.

[0051] The above D 1 and D 2 is preferably -OR from the viewpoint of the molecular weight of the resulting olefin polymer. 15 or -NR 16 R 17 and more preferably -OR 15 is.

[0052] R 15From the viewpoint of the molecular weight of the resulting olefin polymer, 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, a silicon-containing group, or a halogen-containing hydrocarbon group having 2 to 20 carbon atoms, even more preferably a hydrocarbon group having 3 to 20 carbon atoms, still more preferably a linear or branched alkyl group having 3 to 20 carbon atoms or a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and particularly preferably a linear or branched alkyl group having 3 to 10 carbon atoms (e.g., an isopropyl group) or a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms (e.g., a cyclohexyl group). In a preferred embodiment, the R 15 is a linear or branched alkyl group having 3 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 3 to 10 carbon atoms (for example, an isopropyl group). In another preferred embodiment, the R 15 is a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and more preferably a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms (for example, a cyclohexyl group).

[0053] R 16 , R 17 From the viewpoint of the molecular weight of the resulting olefin polymer, each independently 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.

[0054] In the transition metal compound [A], 1 and D 2 -OR 15 or -SR 15 and R 15is a bulky substituent, particularly a hydrocarbon group having two or more carbon atoms, R 15 is a non-bulky substituent, the energy difference between the insertion of a monomer and the chain transfer reaction becomes larger during olefin polymerization, making it more difficult for the chain transfer reaction to occur, and this is presumably why the molecular weight of the olefin polymer is higher. 15 When olefin polymerization is carried out using a transition metal compound [A] in which is a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, preferably a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms (for example, a cyclohexyl group), the molecular weight of the obtained olefin polymer tends to be particularly high.

[0055] 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 Since has two methyl groups, it is presumed that the molecular weight of the olefin polymer increases for the same reason as above.

[0056] However, as the molecular weight of the olefin polymer increases, the entanglement of molecular chains may increase. The degree of entanglement of molecular chains depends not only on the molecular weight of the olefin polymer but also on the bulkiness of the ligand in the compound containing a transition metal atom, particularly on the bulkiness of the ligand near the central metal. 15 In compounds where R is a bulky substituent, especially a hydrocarbon group having two or more carbon atoms, 15 In comparison with compounds in which R is a non-bulky substituent, R has a structure in which the bulky substituent covers the central metal. 15 When olefin polymerization is performed using a compound in which is a bulky substituent, the amount of entanglement of molecular chains in the olefin polymer tends to be small. This is presumably because the crystallization rate is faster than the chain growth rate. In one embodiment, R 15When olefin polymerization is carried out using a transition metal compound [A] in which R is a linear or branched alkyl group having 3 to 20 carbon atoms, preferably a linear or branched alkyl group having 3 to 10 carbon atoms (for example, an isopropyl group), the degree of entanglement of the molecular chains of the resulting olefin polymer tends to be particularly low. When the degree of entanglement of the molecular chains of the olefin polymer is low, the olefin polymer is more likely to exhibit the processability and mechanical properties that the polymer possesses.

[0057] In one embodiment, the R 15 When olefin polymerization is carried out using a transition metal compound [A] in which R is a linear or branched alkyl group having 3 to 20 carbon atoms, preferably a linear or branched alkyl group having 3 to 10 carbon atoms (for example, an isopropyl group), the resulting olefin polymer tends to have an excellent balance between the molecular weight and the degree of entanglement of the molecular chains. When the olefin polymer has an excellent balance between the molecular weight and the degree of entanglement of the molecular chains, the olefin polymer is likely to exhibit the mechanical properties such as impact resistance that the polymer possesses.

[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 15 and D 2 R in 15 and are the same substituents, D 1 R in15 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, and D 1 R in 15 and D 2 R in 15 and are both cyclohexyl 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] 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.

[0060] 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.

[0061] Said L 1 and L 2 is preferably an oxygen atom.

[0062] In the general formula (I), M is a hafnium atom. Hafnium atoms have stronger electrophilicity than zirconium atoms and therefore tend to suppress the β-H elimination reaction. Therefore, it is presumed that the olefin polymer obtained using the transition metal compound [A] has a higher molecular weight than the olefin polymer obtained using a transition metal compound in which M in the general formula (I) is a zirconium atom.

[0063] In general formula (I), D 1 and M, and D 2 The bond between L and M is a coordinate bond, 1 and M, and L 2 The bond between and M is a covalent bond. For example, D 1 -OR 15In 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.

[0064] 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.

[0065] 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.

[0066] The silicon-containing group includes R 1 ~R 9 and R 12 ~R 14Specific 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.

[0067] 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.

[0068] The sulfur-containing group is R 1 ~R 9 and R 12 ~R 14 Specific 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.

[0069] 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.

[0070] 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).

[0071] 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.).

[0072] 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.

[0073] 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.

[0074] Examples of the tin-containing group include R1 ~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.

[0075] 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.

[0076] The X is preferably a halogen atom or a hydrocarbon group, and more preferably a hydrocarbon group having 1 to 30 carbon atoms.

[0077] <Method of producing the transition metal compound [A]> The transition metal compound [A] can be produced, for example, by the following method.

[0078] <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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] Solvent 2 includes, for example, diethyl ether, tetrahydrofuran (THF), tert-butyl methyl ether (TBME), and cyclopentyl methyl ether (CPME).

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] Alkylating agents include, for example, dimethyl sulfate, methyl iodide, dimethyl carbonate, diethyl carbonate, bromopropane, bromobutane, 1-iodopropane, 2-iodopropane, iodoneopentane, iodocyclohexane, and isobutene.

[0093] Examples of the solvent 3 include acetone, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF).

[0094] 2,2'-Dialkoxybiaryls can also be prepared by Suzuki-Miyaura coupling reaction of boronic acids derived from alkoxyaryls with halogenated alkoxyaryls.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] Examples of the alkylating agent include the same alkylating agents as those used in the production of the 2,2'-dialkoxybiaryls.

[0099] 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.

[0100] 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.

[0101] Boronic acid esters include, for example, trimethoxyboronic acid, triethoxyboronic acid, and triisopropoxyboronic acid.

[0102] The method for halogenating the alkoxyaryl may be, for example, a method in which a halogenating agent is allowed to act on the alkoxyaryl.

[0103] Examples of halogenating agents include bromine, N-bromosuccinimide, 1,2-dibromoethane, iodine, N-iodosuccinimide, and 1,2-diiodoethane.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] Examples of solvent 4 include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2-trichloroethane, and 1,1,2,2-tetrachloroethane.

[0108] Examples of the alkyllithium reagent include the same alkyllithium reagents as those used in the production of the 3,3'-dibromo-2,2'-dialkoxybiaryls.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] Commercially available phenols can be used, but in the case of synthesis, they can be obtained, for example, by the Suzuki-Miyaura coupling reaction of a halogenated aromatic compound with an arylboronic acid. Specifically, the solvent 1 is added to a mixture of a halogenated aromatic compound, an arylboronic acid, 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 the compound that serves as a ligand may or may not be added.

[0113] 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.

[0114] Examples of halogenated aromatic compounds 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.

[0115] 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.

[0116] 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.

[0117] Examples of the alkyllithium reagent include the same alkyllithium reagents as those used in the production of the 3,3'-dibromo-2,2'-dialkoxybiaryls.

[0118] 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.

[0119] Phenols can also be obtained by a copper-catalyzed cross-coupling reaction between an aromatic compound and an aryl halide. Specifically, the solvent 1 is added to a mixture of an aromatic compound, an aryl halide, a basic compound, a copper(I) iodide catalyst, and a compound that acts as a ligand for the copper 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. 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] Examples of the alkyllithium reagent include the same alkyllithium reagents as those used in the production of the 3,3'-dibromo-2,2'-dialkoxybiaryls.

[0127] 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.

[0128] The 2,2'-dialkoxybiaryl to be used may be a commercially available product, or may be one produced by the above-mentioned method.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] Examples of the halogenating agent include the same halogenating agents as those used in the halogenation of the alkoxyaryl.

[0135] <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.

[0136] 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.

[0137] 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.

[0138] <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.

[0139] 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], an organoaluminum oxy compound [B-2], and a compound [B-3] that reacts with the transition metal compound [A] to form an ion pair.

[0140] In this specification, an olefin is a hydrocarbon having one or more carbon-carbon double bonds in the molecule.

[0141] As the transition metal compound [A] contained in the olefin polymerization catalyst, the above-mentioned transition metal compound [A] is used.

[0142] The compound [B] preferably used as a constituent component of the olefin polymerization catalyst will be described in detail below.

[0143] [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], an organoaluminum oxy compound [B-2], and a compound [B-3] that reacts with the transition metal compound [A] to form an ion pair.

[0144] The compounds [B-1], [B-2] and [B-3] will be explained below.

[0145] (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.

[0146] R a pAl(OR b ) q H r Y 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.

[0147] Examples of the organoaluminum compound represented by the general formula (B-1a) include the following compounds.

[0148] R a p Al(OR b ) 3-p (wherein 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 (wherein R ais 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.) An organoaluminum compound represented by, R a p AlH 3-p (In the formula, R a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number such that 2 ≤ p < 3.) An organoaluminum compound represented by, and R a p Al(OR b ) q Y s (In the formula, 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 0 < p ≤ 3, q is 0 ≤ q < 3, s is 0 ≤ s < 3, and p + q + s = 3.) An organoaluminum compound represented by.

[0149] Examples of the organoaluminum compound represented by the general formula (B-1a) include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; Tri-branched chain alkylaluminums 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; Tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum and tritolylaluminum; dialkylaluminum hydrides such as diisobutylaluminum hydride; (i-C4H9) x Al 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.

[0150] 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.

[0151] Examples of the compound represented by the general formula (B-1b) include LiAl(C2H5)4, LiAl(C7H 15 )4 can be mentioned.

[0152] 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.

[0153] 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.

[0154] 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].

[0155] The organometallic compounds [B-1] may be used singly or in combination of two or more.

[0156] (Organoaluminum oxy compound [B-2]) The organoaluminum oxy compound [B-2] may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound such as those exemplified in JP-A-2-78687. Examples of the organoaluminum oxy compound [B-2] include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.

[0157] Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent. (1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate, to react the adsorbed water or water of crystallization with the organoaluminum compound. (2) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0158] The aluminoxane may contain a small amount of an organometallic component. After the solvent or unreacted organoaluminum compound is removed by distillation from the recovered aluminoxane solution, the resulting aluminoxane may be redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

[0159] Examples of organoaluminum compounds used in preparing aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compounds represented by the general formula (B-1a) above.

[0160] Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.

[0161] The organoaluminum compounds as described above may be used singly or in combination of two or more.

[0162] Examples of solvents that can be used in preparing aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and diesel; and hydrocarbon solvents such as halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, particularly chlorinated and brominated hydrocarbons. Ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferred.

[0163] The benzene-insoluble organoaluminum oxy-compound used in the present invention is preferably one in which the Al component dissolved in benzene at 60°C is usually 10% or less, preferably 5% or less, and particularly preferably 2% or less, calculated as Al atoms. In other words, it is preferably one which is insoluble or poorly soluble in benzene.

[0164] The organoaluminum oxy compound [B-2] used in the present invention also includes, for example, an organoaluminum oxy compound containing boron represented by the following general formula (II).

[0165] [ka]

[0166] (In general formula (II), R 19 is a hydrocarbon group having 1 to 10 carbon atoms, and four R 20 may be the same or different and are a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.) The boron-containing organoaluminum oxy compound represented by the general formula (II) can be produced by reacting an alkylboronic acid represented by the following general formula (III) with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80° C. to room temperature for 1 minute to 24 hours.

[0167] R 21 -B(OH)2...(III) (in general formula (III), R 21 is R in the general formula (II) 19 It is the same group as Examples of alkylboronic acids represented by the general formula (III) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, and 3,5-bis(trifluoromethyl)phenylboronic acid. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These may be used alone or in combination of two or more.

[0168] Examples of the organoaluminum compound to be reacted with such an alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound represented by the general formula (B-1a) above.

[0169] The organoaluminum compound is preferably a trialkylaluminum or a tricycloalkylaluminum, more preferably trimethylaluminum, triethylaluminum, or triisobutylaluminum, and may be used singly or in combination of two or more.

[0170] The organoaluminum oxy compounds [B-2] may be used singly or in combination of two or more.

[0171] (Compound [B-3] that reacts with transition metal compound [A] to form an ion pair) Examples of the compound [B-3] (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.

[0172] 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.

[0173] Examples of the ionic compound include compounds represented by the following general formula (IV).

[0174] [ka]

[0175] (In general formula (IV), R 22 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 23 ~R 26 may be the same or different and are organic groups, preferably aryl groups or substituted aryl groups.

[0176] Examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0177] 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.

[0178] Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0179] R 22 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.

[0180] Ionic compounds also include, for example, trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0181] 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.

[0182] 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.

[0183] Examples of the dialkylammonium salt include di(1-propyl)ammonium tetra(pentafluorophenyl)boron and dicyclohexylammonium tetra(phenyl)boron.

[0184] 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):

[0185] [ka]

[0186] (In formula (V), Et represents an ethyl group.)

[0187] [ka]

[0188] (In formula (VI), Et represents an ethyl group.)

[0189] Examples of borane compounds, which are ionizable ionic compounds (compound [B-3]), 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).

[0190] 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).

[0191] 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.

[0192] 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.

[0193] The compound [B-3] may be used singly or in combination of two or more.

[0194] When an organoaluminum oxy compound [B-2] such as methylaluminoxane is used as a co-catalyst component in addition to the transition metal compound [A], it shows extremely high polymerization activity for olefin compounds.

[0195] 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], an organoaluminum oxy compound [B-2], and a compound [B-3], and, if necessary, a support [C] as follows:

[0196] [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.

[0197] 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.

[0198] 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.

[0199] 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.

[0200] 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 700m 2 / 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.

[0201] 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.

[0202] 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.

[0203] 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.

[0204] 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).

[0205] 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.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] 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.

[0210] The solid organoaluminum oxy-compound is a solid component obtained by insolubilizing the organoaluminum oxy-compound [B-2], 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.

[0211] 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.

[0212] 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.

[0213] [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.

[0214] The alcohols and phenolic compounds are generally selected from the group consisting of R 27 -OH, where R 27 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).

[0215] As for alcohols, R 28 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.

[0216] The carboxylic acid is usually R 28The one represented by -COOH is used. 28 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.

[0217] 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.

[0218] <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.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] 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.

[0223] 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.

[0224] The organometallic compound [B-1] is used in an amount such that the molar ratio of the organometallic compound [B-1] to all transition metal atoms (M) in the transition metal compound [A] ([B-1] / M) is usually 0.01 to 200,000, preferably 0.05 to 100,000, more preferably 1.0 to 50,000, and even more preferably 200 to 40,000. The organoaluminum oxy compound [B-2] is used in an amount such that the molar ratio of the aluminum atoms in the organoaluminum oxy compound [B-2] to all transition metals (M) in the transition metal compound [A] ([B-2] / M) is usually 10 to 500,000, preferably 20 to 100,000, more preferably 100 to 50,000, even more preferably 150 to 25,000, and particularly preferably 200 to 16,000. The compound (ionizing ionic compound) [B-3] that reacts with the transition metal compound [A] to form an ion pair is used in an amount such that the molar ratio of the compound [B-3] to the transition metal atom (M) in the transition metal compound [A] ([B-3] / M) is usually 1 to 1,000, preferably 1 to 500, more preferably 1 to 20, even more preferably 1 to 10, and particularly preferably 1 to 4.

[0225] 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 an organoaluminum oxy compound [B-2], organic compound component [D] is used in an amount such that the molar ratio of organic compound component [D] to organoaluminum oxy compound [B-2] ([D] / [B-2]) is usually 0.001 to 20, preferably 0.005 to 10. When compound [B] is compound [B-3], organic compound component [D] is used in an amount such that the molar ratio of organic compound component [D] to compound [B-3] ([D] / [B-3]) is usually 0.01 to 100, preferably 0.1 to 50.

[0226] 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, more preferably 0 to 80°C, even more preferably 0 to 50°C, and particularly preferably 0 to 30°C. When olefin polymerization is carried out under low-temperature conditions (for example, 30°C or lower), the crystallization rate tends to be higher than the chain growth rate in olefin polymerization using the transition metal compound [A]. Therefore, the amount of entanglement of molecular chains in the olefin polymer tends to be low. 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.

[0227] 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.

[0228] 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.

[0229] 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").

[0230] 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.

[0231] 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.

[0232] 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]

[0233] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples.

[0234] [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).

[0235] [Polymer weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC) using a Waters Alliance GPC 2000 gel permeation chromatograph (high-temperature size exclusion chromatograph) under the following operating conditions: (Operating conditions) Measurement equipment: Gel permeation chromatograph Alliance GPC2000 (Waters) Analysis software: Chromatography Data System Empower (trademark, manufactured by Waters) Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HT x 2 (inner diameter 7.5 mm x length 30 cm, manufactured by Tosoh Corporation) Mobile phase: o-dichlorobenzene (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Detector: Differential refractometer (built into the device) Column temperature: 140℃ Flow rate: 1.0mL / min Injection volume: 400μL Sampling time interval: 1 second Sample concentration: 0.15% (w / v) Molecular weight calibration: Monodisperse polystyrene (manufactured by Tosoh Corporation) / molecular weight 495 to 20.6 million

[0236] [Intrinsic viscosity [η]] The intrinsic viscosity [η] of the olefin polymer was measured using a fully automatic intrinsic viscometer manufactured by Rigo Co., Ltd. at a temperature of 135° C. and in decalin as a measurement solvent.

[0237] [Synthesis Example 1] In a thoroughly dried 300 mL three-neck flask, 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) were added under a nitrogen atmosphere and stirred under reflux for 72 hours. After the reaction, the mixture was extracted twice with ethyl acetate, and 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 obtain 5.90 g of compound (1) (yield: 96%). The product was confirmed by measuring the GC-MS spectrum.

[0238] [ka]

[0239] [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. Then, 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 compound (2) was concentrated using a rotary evaporator and used directly in the next reaction.

[0240] [ka]

[0241] [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) (yield 90%). The target substance was confirmed by measuring the GC-MS spectrum.

[0242] [ka]

[0243] [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 the mixture was allowed to react 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) (43% yield). 1 H 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).

[0244] [ka]

[0245] [Synthesis Example 5] 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 containing compound (5) (yield 104%). MOM in compound (5) means a methoxymethyl group.

[0246] 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).

[0247] [ka]

[0248] [Synthesis Example 6] A thoroughly dried 200 mL three-neck flask was charged with 3.22 g (0.0033 mol) of compound (5), 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 using a rotary evaporator was purified using a silica gel column (hexane:methylene chloride = 1:1), yielding 1.94 g of compound (6). (Yield: 66%)

[0249] 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).

[0250] [ka]

[0251] [Example 1] In a thoroughly dried 100 mL Schlenk tube, 0.074 g (0.23 mmol) of hafnium(IV) chloride (1 equivalent relative to compound (6)) was weighed out under a nitrogen atmosphere, and 30 mL of dehydrated toluene was added 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. The reaction solution was white at this time. In a thoroughly dried 100 mL Schlenk tube, 0.200 g (0.23 mmol) of compound (6) was weighed out under a nitrogen atmosphere, and 15 mL of toluene was added and stirred at -78 °C. The solution was stirred overnight at -78 °C to room temperature. The color of the reaction solution gradually changed from white to pale yellow. After the reaction, the solution was concentrated using a vacuum pump and placed in a glove box. Toluene was added to this concentrated solid, thoroughly stirred, and filtered through a 1.0 μm filter to remove insoluble matter. The filtrate was concentrated using a rotary evaporator, and recrystallization was carried out twice by adding hexane / toluene and leaving it in a freezer (-40°C). Since the target product and impurities (0.361 g pale yellow solid) were observed in the filtrate, the amount of toluene was reduced and the filtrate was left in a freezer (-40°C) overnight again, yielding 0.138 g of compound (A) in the precipitate (yield 55%).

[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] [Comparative Example 1] 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 (6) and 20 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 for approximately 5 minutes until the mixture turned 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 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, added hexane, and cooled overnight. The precipitated solid was filtered off, yielding 143.6 mg of compound (A'). (63% yield)

[0255] 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).

[0256] [ka]

[0257] [Synthesis Example 7] A 300 mL three-neck flask was thoroughly dried and purged with nitrogen. 25.0 g (231 mmol) of p-cresol and 50 mL of dichloromethane (DCM) were placed in the flask and cooled to 0°C. 79.4 mL (462 mmol) of N,N-diisopropylethylamine was added dropwise and stirred at 0°C for 1 hour. 54.9 mL (693 mmol) of chloromethyl methyl ether was then slowly added dropwise and allowed to react overnight at room temperature. Distilled water was added, followed by neutralization with 1N HCl. Extraction was performed three times with DCM. The organic layer was washed with saturated aqueous ammonium chloride, saturated sodium bicarbonate, and saturated saline, and then dried over magnesium sulfate. The magnesium sulfate was removed by filtration. The filtrate was evaporated, and compound (7) was obtained by silica gel column chromatography (hexane / ethyl acetate (20 / 1)) in a 91% yield. MOM in compound (7) means a methoxymethyl group.

[0258] 1 H NMR(400MHz,CDCl3,δ in ppm)7.10-7.07(2H,d,J=8.2Hz),6.94-6.92(2H,d,J=8.3Hz),6.49(1H,s),5.14(2H,s),3.47(3H,s),2.29(3H,s).

[0259] [ka]

[0260] [Synthesis Example 8] A 300 mL three-neck flask was thoroughly dried and purged with nitrogen. 16.0 g (105 mmol) of compound (7) and 150 mL of THF were placed in the flask and cooled to 0°C. 85.4 mL of n-butyllithium solution (hexane solution, 1.6 M, 137 mmol) was added and stirred at 0°C for 1 hour. 15.5 mL (105 mmol) of trimethoxyborane was slowly added dropwise to the reaction mixture, and the mixture was allowed to react overnight at room temperature. Distilled water was added, followed by neutralization with 2N HCl. The mixture was then extracted three times with ethyl acetate. The mixture was washed with saturated aqueous ammonium chloride, saturated sodium bicarbonate, and saturated saline, and the resulting organic layer was dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the filtrate was evaporated. The solid and liquid were then separated by filtration. The solid was washed with hexane to obtain compound (8) (yield: 22%).

[0261] 1 H NMR(400MHz,CDCl3,δ in ppm)7.65(1H,s),7.23-7.21.(1H,dd,J=6.8Hz),7.04-7.01.(1H,d,J=8.5Hz),5.89(2H,s),5.23(2H,s),3.50(3H,s),2.31(3H,s).

[0262] [ka]

[0263] [Synthesis Example 9] A 300 mL three-neck flask was thoroughly dried and purged with nitrogen. 9.00 g (45.9 mmol) of compound (8), 12.4 g (45.9 mmol) of 1-bromo-3,5-di-t-butylbenzene, 0.412 g (1.84 mmol) of Pd(OAc)2, 1.51 g (3.67 mmol) of Sphos, 14.6 g (138 mmol) of sodium carbonate, and 75 mL of THF were charged and stirred. 50 mL of distilled water was slowly added dropwise at room temperature, and the mixture was refluxed overnight. While cooling in an ice bath, saturated aqueous ammonium chloride was added, followed by extraction three times with ethyl acetate. The resulting organic layer was washed with saturated aqueous ammonium chloride, saturated sodium bicarbonate, and saturated brine, and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the filtrate was evaporated. Compound (9) was obtained by column chromatography (hexane / ethyl acetate (100 / 1)) in an 89% yield.

[0264] 1 H NMR(400MHz,CDCl3,δ in ppm)7.38(1H,s),7.36(2H,m),7.16(1H,s),7.12-7.07(2H,m),5.06(2H,s),3.38(3H,s),2.35(3H,s),1.36(18H,s).

[0265] [ka]

[0266] [Synthesis Example 10] A 100 mL three-neck flask was thoroughly dried and purged with nitrogen. 7.00 g (20.6 mmol) of compound (9) and 35 mL of THF were placed in the flask and cooled to 0°C. 15.4 mL of n-butyllithium solution (hexane solution, 1.6 M, 24.7 mmol) was added and stirred at 0°C for 1 hour. 3.50 mL (30.8 mmol) of trimethoxyborane was slowly added dropwise to the reaction mixture, and the mixture was allowed to react overnight at room temperature. Distilled water was added, followed by neutralization with 2N HCl. The mixture was then extracted three times with ethyl acetate. The mixture was washed with saturated aqueous ammonium chloride, saturated sodium bicarbonate, and saturated saline, and the resulting organic layer was dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the filtrate was evaporated. The solid and liquid were separated by filtration. The solid was washed with hexane to obtain compound (10). (Yield: 50%)

[0267] 1 H NMR(400MHz,CDCl3,δ in ppm)7.61(1H,d),7.39(1H,t),7.35-7.34(2H,d),7.24-7.27(2H,m),5.99(2H,s),4.52(2H,s).3.23(3H,s),2.38(3H,s),1.36(18H,s).

[0268] [ka]

[0269] [Synthesis Example 11] A 100 mL three-neck flask was thoroughly dried and purged with nitrogen. 0.365 g (0.951 mmol) of compound (10), 10 mL of DCM, and 10 mL of MeOH were placed in the flask and cooled to 0 °C. 10 mL (60 mmol) of 6 N HCl was added and the mixture was allowed to react overnight at room temperature. While cooling in an ice bath, saturated sodium bicarbonate solution was added to neutralize the mixture, followed by extraction with ethyl acetate three times. The mixture was washed with saturated aqueous ammonium chloride, saturated sodium bicarbonate, and saturated brine, and the resulting organic layer was dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the filtrate was evaporated. The solid was then washed with hexane to obtain a mixture containing compound (11). This compound was used in the next step in this state.

[0270] [ka]

[0271] [Synthesis Example 12] A thoroughly dried, nitrogen-purged 200 mL three-neck flask was charged with 6.72 g (32 mmol) of cyclohexane iodide, 10.43 g (32 mmol) of cesium carbonate, 2.98 g (8.0 mmol) of 3,3'-dibromo-2,2'-dihydroxy-5,5'-dimethyl-1,1'-biphenyl, and 100 mL of DMF, and the mixture was allowed to react overnight at 100 °C. While cooling in an ice bath, saturated aqueous ammonium chloride solution was added, followed by extraction three times with ethyl acetate. After washing with water and saturated brine, the resulting organic layer was dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the filtrate was evaporated. Compound (12) was obtained by column chromatography (hexane / ethyl acetate (300 / 1)) in a 28% yield. Cy in the compound (12) represents a cyclohexyl group.

[0272] 1 H NMR(400MHz,CDCl3,δ in ppm)7.34(2H,dd,J=2.0Hz,0.8Hz),7.29(2H,dd,J=2.0Hz,0.8Hz),3.60-3.54(2H,m),2.28(6H,s),1.69-1.62(8H,m),1.45-0.88(12H,m).

[0273] [ka]

[0274] [Synthesis Example 13] A 200 mL three-neck flask was thoroughly dried and purged with nitrogen. 0.289 g (0.539 mmol) of compound (11), 0.385 g (1.13 mmol) of compound (12), 4.84 mg (21.6 μmol) of Pd(OAc)2, 17.7 mg (43.1 μmol) of Sphos, 0.686 g (138 mmol) of tripotassium phosphate, and 70 mL of THF were charged and stirred. 7 mL of distilled water was slowly added dropwise at room temperature, and the mixture was refluxed overnight. While cooling in an ice bath, saturated aqueous ammonium chloride was added, followed by extraction three times with ethyl acetate. The resulting organic layer was washed with saturated aqueous ammonium chloride, saturated sodium bicarbonate, and saturated brine, and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the filtrate was evaporated. Compound (13) was obtained by column chromatography (hexane / ethyl acetate (50 / 1)) in a 69% yield.

[0275] 1 H NMR(400MHz,CDCl3,δ in ppm)7.40-7.15(14H,m),3.57(1H,s),3.40(1H,s),2.42-2.28(12H),1.66-0.87(56H,m).

[0276] [ka]

[0277] [Example 2] In a thoroughly dried 100 mL Schlenk tube, 0.039 g (0.12 mmol) of hafnium(IV) chloride and 15 mL of dehydrated toluene were added under a nitrogen atmosphere and stirred at -78 °C. 0.16 mL (0.49 mmol) of MeMgBr (3 M ether solution) was slowly added and stirred at -40 °C for 1 hour. 0.118 g (0.12 mmol) of compound (13) in toluene was added dropwise to this solution at -78 °C. The reaction solution was warmed to room temperature and stirred overnight. After the reaction, insoluble matter was removed using a 0.45 μm filter. The filtrate was concentrated and washed with hexane to obtain compound (B) as a white solid (yield 59%).

[0278] 1 H NMR(400MHz,C6D6,δ in ppm)7.66(s,4H),7.49(t,J=1.6Hz,2H),7.42(d,J=2.0Hz,2H),7.29(d,J=2.4Hz,2H),7.11(d,J=2.0Hz,2H),7.0 4(d,J=2.4Hz,2H),3.51-3.59(m,2H),2.37(s,6H),2.23(s,6H),1.85-0.58(m,20H),1.43(s,36H),-0.33(s,6H).

[0279] [ka]

[0280] <Production of ethylene polymer> [Example 3] 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 of triisobutylaluminum (TIBA), followed by 0.05 μmol of compound (A) obtained in Example 1 and 0.2 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate (TrB). Ethylene was continuously supplied at 100 L / hr, and polymerization was carried out at 25°C under atmospheric pressure for 5 minutes. The polymerization was then terminated by adding a small amount of methanol. After polymerization, the mixture was added to 750 mL of methanol containing 2 mL of hydrochloric acid, stirred for at least 30 minutes, and then filtered. The resulting polymer was further dried under reduced pressure at 80°C for 10 hours. The resulting polyethylene yield was 0.691 g, and the [η] was 16.51 dL / g. The results are shown in Table 1.

[0281] [Examples 4 to 5, 9 to 11 and Comparative Examples 2 to 4] Ethylene polymerization was carried out in the same manner as in Example 3, except that the compounds shown in Table 1 were used and the polymerization conditions were changed as shown in Table 1. The results are shown in Table 1.

[0282] [Example 6] 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 polymethylaluminoxane (PMAO) followed by 0.1 μmol of compound (A) obtained in Example 1. Ethylene was continuously supplied at 100 L / hr, and polymerization was carried out at 25°C under atmospheric pressure for 5 minutes. The polymerization was then terminated by adding a small amount of methanol. After polymerization was completed, the mixture was added to 750 mL of methanol containing 2 mL of hydrochloric acid, stirred for at least 30 minutes, and then filtered. The resulting polymer was further dried under reduced pressure at 80°C for 10 hours. The resulting polyethylene yield was 0.385 g, and the [η] was 13.24 dL / g. The results are shown in Table 1.

[0283] [Examples 7 to 8, 12 to 14 and Comparative Examples 5 to 7] Ethylene polymerization was carried out in the same manner as in Example 6, except that the compounds shown in Table 1 were used and the polymerization conditions were changed as shown in Table 1. The results are shown in Table 1.

[0284] [Table 1]

[0285] In Table 1, PMAO represents polymethylaluminoxane, TrB represents triphenylcarbenium tetrakis(pentafluorophenyl)borate, and TIBA represents triisobutylaluminum.

[0286] [Example 15] 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 0.35 mmol (calculated as aluminum atoms) of polymethylaluminoxane and 0.30 μmol of the compound (A). Ethylene was continuously supplied at 100 L / hr, and polymerization was carried out for 30 minutes at an internal temperature of 10°C under atmospheric pressure. The polymerization was then terminated by adding 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 1.901 g of ethylene polymer.

[0287] [Evaluation of the degree of entanglement of molecular chains] The degree of entanglement of molecular chains was evaluated by annealing measurement using a differential scanning calorimeter (DSC). The annealing measurement using DSC was carried out as follows under a nitrogen atmosphere using approximately 5 mg of the ethylene polymers obtained in Examples 9 and 15. First, the temperature was increased from 30°C to 138°C at a rate of 10°C / min and held for 180 minutes. Next, the temperature was decreased from 138°C to 30°C at a rate of 10°C / min and held for 10 minutes. Finally, the temperature was increased from 30°C to 200°C at a rate of 10°C / min for the second time.

[0288] The analysis was performed by dividing the valley of the curve obtained from the second heating (second heating curve) by integral division, and entanglement was evaluated based on the results. Note that integral division refers to dividing the peak area (integral value) of the obtained DSC curve into multiple components. In the above analysis, the second heating curve was divided vertically in half at the position of the maximum point between the two peaks (area division temperature), and the peak area was divided in half. The melting point of the lower-melting peak of the two peaks was designated Tm1, the area of ​​the lower-melting peak was designated ΔHm1, the melting point of the higher-melting peak was designated Tm2, ​​and the area of ​​the higher-melting peak was designated ΔHm2. The proportion of melt-crystallized form was calculated as ΔHm1 / (ΔHm1+ΔHm2). To compare the balance between molecular weight and the degree of entanglement of molecular chains in ethylene polymers with different molecular weights (intrinsic viscosity), a balance index log[η]×ΔHm1 / (ΔHm1+ΔHm2) was set using the proportion of melt-crystallized form. The measurement results are shown in Table 2 and Figures 1 and 2.

[0289] [Table 2]

[0290] ΔHm1 represents the area of ​​the peak derived from the crystalline component with less entanglement of molecular chains, and ΔHm2 represents the area of ​​the peak derived from the crystalline component with more entanglement of molecular chains. Therefore, in Table 2, the larger the proportion of melt-crystallized form ΔHm1 / (ΔHm1+ΔHm2), the less entanglement of molecular chains in the ethylene polymer. Also, the larger the balance index log[η]×ΔHm1 / (ΔHm1+ΔHm2), the more likely it is that a transition metal compound will give an ethylene polymer with less entanglement of molecular chains, even if the molecular weight is high.

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 are each independently 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; 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, 【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 hafnium atom; 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 The transition metal compound [A] according to claim 1, wherein each of the groups independently represents a hydrocarbon group.

3. The above D １ and D ２ are each independently -OR １５ and R １５ is a hydrocarbon group having 2 to 20 carbon atoms, a silicon-containing group, or a halogen-containing hydrocarbon group.

4. The R １５ is a hydrocarbon group having 3 to 20 carbon atoms.

5. The R １５ is a linear or branched alkyl group having 3 to 20 carbon atoms.

6. The R １５ is a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms.

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

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

9. Organometallic compound [B-1], an organoaluminum oxy compound [B-2], and The olefin polymerization catalyst according to claim 8, further comprising at least one compound [B] selected from the group consisting of compounds [B-3] that react with the transition metal compound [A] to form an ion pair.

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

11. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 8.

12. The method for producing an olefin polymer according to claim 11, 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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