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

Abstract

To provide a novel transition metal compound useful for a catalyst for olefin polymerization that shows superior performance in production of olefin polymers; for example, it has high polymerization activity and, in olefin copolymerization, has high polymerization activity and excellent copolymerization reactivity.SOLUTION: The present invention provides a transition metal compound (A) represented by general formula (1) (In general formula (1), M is a transition metal atom of groups 3-10 in the periodic table, R1-R13 each denote a hydrogen atom, a hydrocarbon group or the like, Y is an oxygen atom or the like, n is a valence of M, X is a halogen atom or the like).SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Conventionally, known catalysts for producing olefin polymers such as ethylene polymers and ethylene-α-olefin copolymers include titanium-based catalysts consisting of titanium compounds and organoaluminum compounds, and vanadium-based catalysts consisting of vanadium compounds and organoaluminum compounds. Metallocene-based catalysts consisting of metallocene compounds such as zirconocene and organoaluminum oxy compounds (aluminoxanes) are also known as catalysts capable of producing olefin polymers with high polymerization activity.

[0003] 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 very 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 there are few examples of their industrial use.

[0004] On the other hand, the present applicant has already found that transition metal compounds having a phenoxyimine ligand can enhance the activity of olefin polymerization catalysts and impart various functions and features to the olefin polymers obtained thereby by converting the ligand skeleton or substituents (e.g., Non-Patent Document 2). [Prior art documents] [Non-patent literature]

[0005] [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]

[0006] As mentioned above, there are few examples of multidentate postmetallocene catalysts being used at an industrial level. In order to be used at an industrial level, it will be important that the catalyst has the performance to show the effect specific to multidentate postmetallocene catalysts, in addition to the effect of conventional indicators such as polymerization activity.

[0007] When multiple olefins are copolymerized, the copolymerization reactivity of each olefin often differs. In particular, ethylene often has extremely high polymerization reactivity compared to other olefins. Specifically, it is known that olefins with a small number of carbon atoms and low bulkiness tend to show high copolymerization reactivity. For this reason, especially when an olefin copolymer is produced by a batch polymerization process, there may be a risk of the composition distribution spreading. In a continuous polymerization process, the risk of the composition distribution spreading can be suppressed by process control technology, but the control of the gas composition when recovering and using the unreacted olefin often requires advanced management. Therefore, a catalyst that can improve the copolymerization reactivity of olefins during copolymerization is considered to have great industrial merits. For example, when a copolymer is produced by copolymerization of ethylene and propylene, if the reactivity of ethylene and propylene is the same, the composition of the unreacted olefin gas will be the same as the composition of the olefin gas supplied to the reaction, which is considered to be a great advantage in controlling the copolymerization and stabilizing the production process.

[0008] Of course, even if the copolymerization reactivities are not equal, simply being able to reduce the difference will bring about advantages in controlling the copolymerization reaction and stabilizing the production process compared to the conventional techniques. Accordingly, an object of the present invention is to provide an olefin polymerization catalyst which exhibits superior performance in the production of olefin polymers, such as having high polymerization activity and, in olefin copolymerization, having high polymerization activity and excellent copolymerization reactivity (in the present invention, "excellent copolymerization reactivity" means that there is a small difference in copolymerization reactivity between different olefins), a novel transition metal compound for use in such an olefin polymerization catalyst, an olefin polymerization catalyst containing this transition metal compound, and a method for producing an olefin polymer using this catalyst. [Means for solving the problem]

[0009] As a result of intensive research by the present inventors to achieve the above object, they have found that an olefin polymerization catalyst containing a specific transition metal compound having a multidentate ligand having an oxygen atom derived from a phenoxy group, a nitrogen atom derived from an amino group, and an additional donor atom (such as an oxygen atom) exhibits high olefin polymerization activity, and in olefin copolymerization, exhibits high olefin polymerization activity as well as excellent copolymerization reactivity, and have completed the present invention. That is, the present invention relates to the following [1] to [6].

[0010] [1] A transition metal compound (A) represented by the following general formula (1):

[0011] [ka] (In the general formula (1), M represents a transition metal atom of Groups 3 to 10 of the periodic table. R 1 ~R 13 may be the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group; R 1 ~R 13 Two or more of these may be linked to each other to form a ring, and the ring may further have the above-mentioned substituents.

[0012] Y is an oxygen atom, a sulfur atom, or -N(-R 14 )-represented by the structure (R 14 represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. The straight lines at the left and right ends represent bonds between the nitrogen atom and the adjacent carbon atom. n indicates the valence of M. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when there are a plurality of X's, they may be the same or different, and two or more X's may be linked together to form a ring.

[0013] [2] The transition metal compound (A) according to the above [1], wherein in the above general formula (1), M is a transition metal atom of Group 4 of the periodic table, and n is 4. [3] The transition metal compound (A) of the above [1] or [2], wherein Y in the above general formula (1) is an oxygen atom. [4] A catalyst for olefin polymerization comprising the transition metal compound (A) according to any one of [1] to [3] above. [5](B)(B-1) Organometallic compound (B-2) an organoaluminum oxy compound, and (B-3) A compound that reacts with the transition metal compound (A) to form an ion pair The olefin polymerization catalyst according to [4] above, further comprising at least one compound selected from the group consisting of: [6] A method for producing an olefin polymer, comprising homopolymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to [4] or [5] above. In the present invention, the term "polymerization" is used to include both "homopolymerization" and "copolymerization". Furthermore, the term "polymer" is used to include both "homopolymer" and "copolymer". Effect of the Invention

[0014] The transition metal compound of the present invention has a ligand which has a chemically stable phenoxy structure or amine structure having excellent electron donating / accepting ability, and has a three-dimensional structure having a structure having excellent electron donating / accepting ability (the structure represented by Y in general formula (1)). Therefore, an olefin polymerization catalyst containing this transition metal compound exhibits high olefin polymerization activity, and in olefin copolymerization, it exhibits high olefin polymerization activity as well as excellent copolymerization reactivity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] <Transition metal compound (A)> The transition metal compound of the present invention (hereinafter referred to as "transition metal compound (A)") is represented by the following general formula (1).

[0016] [ka]

[0017] In general formula (1), M is a transition metal atom of Groups 3 to 10 of the periodic table (Group 3 also includes lanthanoids), preferably a transition metal atom of Groups 3 to 9 (Group 3 also includes lanthanoids), more preferably a transition metal atom of Groups 3 to 6 (Group 3 also includes lanthanoids), particularly preferably a transition metal atom of Groups 4 to 6, and most preferably a transition metal atom of Group 4. Specifically, the metal atom includes a scandium atom, a yttrium atom, a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a niobium atom, a tantalum atom, a chromium atom, a molybdenum atom, a tungsten atom, a manganese atom, a rhenium atom, an iron atom, a ruthenium atom, a cobalt atom, a rhodium atom, an iridium atom, a nickel atom, a palladium atom, and a platinum atom. The metal atom is preferably a scandium atom, a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a niobium atom, a tantalum atom, a chromium atom, a molybdenum atom, a tungsten atom, a cobalt atom, a rhodium atom, and an iridium atom. The metal atom is more preferably a titanium atom, a zirconium atom, a hafnium atom, a vanadium atom, a niobium atom, a tantalum atom, a chromium atom, a molybdenum atom, and a tungsten atom. The metal atom is particularly preferably a titanium atom, a zirconium atom, a hafnium atom, a chromium atom, and a tantalum atom. The metal atom is most preferably a titanium atom, a zirconium atom, and a hafnium atom.

[0018] In the general formula (1), R 1 ~R 13 may be the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group; R 1 ~R 13 may be bonded to each other to form a ring, and the ring may further have the above-mentioned substituents. Note that the scope of these substituents may overlap with each other, for example, a pyridinyl group is included in both the heterocyclic compound residue and the nitrogen-containing group.

[0019] Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group include: linear or branched alkyl groups having 1 to 30, 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, a neopentyl group, or an n-hexyl group; linear or branched alkenyl groups having 2 to 30, preferably 2 to 20, carbon atoms, such as a vinyl group, an allyl group, or an isopropenyl group; linear or branched alkynyl groups having 2 to 30, preferably 2 to 20, carbon atoms, such as an ethynyl group or 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 cyclohexyl group, or an adamantyl group; Cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms, such as cyclopentadienyl groups, indenyl groups, and fluorenyl groups; and Examples of the aryl group include aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group.

[0020] In the hydrocarbon group, a hydrogen atom may be substituted with a halogen. Examples of the hydrocarbon group in which a hydrogen atom is substituted with a halogen include halogenated hydrocarbon groups having 1 to 30, preferably 1 to 20, carbon atoms, such as a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group.

[0021] In addition, in the alkyl group, alkenyl group, alkynyl group, cyclic saturated hydrocarbon group, cyclic unsaturated hydrocarbon group, and aryl group, a hydrogen atom may be substituted with another hydrocarbon group. Examples of such hydrocarbon groups in which a hydrogen atom is substituted with a hydrocarbon group include aryl group-substituted alkyl groups such as a benzyl group, a cumyl group, and a trityl group; and alkyl-substituted aryl groups such as a tolyl group, an isopropylphenyl group, a tert-butylphenyl group, a dimethylphenyl group, a di-tert-butylphenyl group, and a tri-isopropylphenyl group.

[0022] Furthermore, the hydrocarbon group is Heterocyclic compound residues; Oxygen-containing groups such as alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, and carboxylic anhydride groups; nitrogen-containing groups such as amino groups, imino groups, amido groups, imido groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and amino groups in the form of ammonium salts; boron-containing groups such as boranediyl, boranetriyl, and diboranyl groups; sulfur-containing groups such as 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, and a sulfenyl group; Phosphorus-containing groups such as phosphido groups, phosphoryl groups, thiophosphoryl groups, and phosphato groups; Silicon-containing groups; a germanium-containing group; or Tin-containing groups

[0043]

[0023] Specific examples of the heterocyclic compound residue include residues obtained by removing one hydrogen atom from nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, triazine, carbazole, and phenanthroline; oxygen-containing compounds such as furan, pyran, benzofuran, and benzopyran; and sulfur-containing compounds such as thiophene and benzothiophene; and groups in which the hydrogen atom of these heterocyclic compound residues is further substituted with a substituent having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as an alkyl group, an alkoxy group, or an aryl group.

[0024] Examples of the silicon-containing group include silyl group, siloxy group, hydrocarbon-substituted silyl group, and hydrocarbon-substituted siloxy group, and more specifically, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-tert-butylsilyl group, dimethyl(pentafluorophenyl)silyl group, and tribenzylsilyl group. Among these, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, triphenylsilyl group, and tribenzylsilyl group are preferred, and particularly preferred are trimethylsilyl group, triethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, and tribenzylsilyl group. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group, a triethylsiloxy group, a triphenylsiloxy group, and a tribenzylsiloxy group.

[0025] 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. R 1 ~R 13 As described above, examples of the alkyl group include oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups and tin-containing groups, and examples of these include the same groups as those exemplified as the groups that the hydrocarbon group may have.

[0026] Among the oxygen-containing groups, specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group. Specific 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. Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group. Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group.

[0027] Among the nitrogen-containing groups, specific examples of amino groups include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group; specific examples of imino groups include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, and a phenylimino group; specific examples of amide groups include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group; and specific examples of imide groups include an acetimide group and a benzimide group.

[0028] Among the sulfur-containing groups, specific examples of thioester groups include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, a phenylthiocarbonyl group, etc.; specific examples of alkylthio groups include a methylthio group, an ethylthio group, etc.; specific examples of arylthio groups include a phenylthio group, a methylphenylthio group, a naphthylthio group, etc.; specific examples of sulfone ester groups include a methyl sulfonate group, an ethyl sulfonate group, a phenyl sulfonate group, etc.; and specific examples of sulfonamide groups include a phenylsulfonamide group, an N-methylsulfonamide group, an N-methyl-p-toluenesulfonamide group, etc.

[0029] R 1 ~R 13is preferably a hydrogen atom, a hydrocarbon group, or a heterocyclic compound residue, and more preferably a hydrogen atom or a hydrocarbon group. linear or branched alkyl groups having 1 to 30, 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, a neopentyl group, or an n-hexyl group; aryl groups having 6 to 30, preferably 6 to 20, carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group; Preferred are substituted aryl groups in which 1 to 5 hydrogen atoms of these aryl groups are substituted with a substituent such as a halogen atom, an alkyl or alkoxy group having 1 to 30, preferably 1 to 20, carbon atoms, or an aryloxy group having 6 to 30, preferably 6 to 20, carbon atoms.

[0030] Particularly preferred examples of the heterocyclic compound residue include residues obtained by removing one hydrogen atom from nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, triazine, carbazole, and phenanthroline; oxygen-containing compounds such as furan, pyran, benzofuran, and benzopyran; and sulfur-containing compounds such as thiophene and benzothiophene; and groups in which the hydrogen atom of these heterocyclic compound residues is substituted with a substituent such as an alkyl or alkoxy group having 1 to 30, preferably 1 to 20, carbon atoms, or an aryl group having 6 to 30, preferably 6 to 20, carbon atoms.

[0031] R in general formula (1) 1 ~R 13 Two or more of the groups may be linked together to form a ring. More specifically, R 1 ~R 13 Two or more of these groups, preferably adjacent groups, may be linked to each other to form a ring such as an aliphatic ring, an aromatic ring, or a heterocycle containing a heteroatom such as a nitrogen atom, and these rings may further have a substituent.

[0032] In the general formula (1), Y is an oxygen atom, a sulfur atom, or -N(-R 14 The structure represented by the formula: R 14 The definition of R 1 ~R 13 is the same as R 14 As for R 1 ~R 13 The same substituents as those exemplified in can be selected, and a hydrocarbon group is preferable. An oxygen atom is particularly preferable as Y.

[0033] In general formula (1), X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group.

[0034] Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group include R 1 ~R 13 Examples of the hydrocarbon groups include the same groups as those exemplified in 1. Specifically, the examples include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl; alkenyl groups such as vinyl, propenyl, and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, and phenylpropyl; and aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, and phenanthryl. These hydrocarbon groups also include halogenated hydrocarbon groups, specifically, groups in which at least one hydrogen atom of a hydrocarbon group having 1 to 20 carbon atoms is substituted with a halogen. Among these, the halogenated hydrocarbon group is preferably a halogenated hydrocarbon group having 1 to 10 carbon atoms.

[0035] Specific examples of the oxygen-containing group 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; and a carbonyl group.

[0036] Specific examples of the sulfur-containing group include R 1 ~R 13 Specific examples of the sulfonate group include sulfonate groups such as a methylsulfonate group, a trifluoromethanesulfonate group, a phenylsulfonate group, a benzylsulfonate group, a p-toluenesulfonate group, a trimethylbenzenesulfonate group, a triisobutylbenzenesulfonate group, a p-chlorobenzenesulfonate group, and a pentafluorobenzenesulfonate group; sulfinate groups such as a methylsulfinate group, a phenylsulfinate group, a benzylsulfinate group, a p-toluenesulfinate group, a trimethylbenzenesulfinate group, and a pentafluorobenzenesulfinate group; an alkylthio group; and an arylthio group.

[0037] Specific examples of the nitrogen-containing group include R 1 ~R 13 Specific examples of the amino group include alkylamino groups such as methylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, and dicyclohexylamino group, and arylamino groups or alkylarylamino groups such as phenylamino group, diphenylamino group, ditolylamino group, dinaphthylamino group, and methylphenylamino group.

[0038] Specific examples of the boron-containing group include BR4 (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like). Specific examples of the aluminum-containing group include AlR4 (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

[0039] Specific examples of the phosphorus-containing group include trialkylphosphine groups such as a trimethylphosphine group, a tributylphosphine group, and a tricyclohexylphosphine group; triarylphosphine groups such as a triphenylphosphine group and a tritolylphosphine group; phosphite groups (phosphido groups) such as a methylphosphine group, an ethylphosphine group, and a phenylphosphine group; phosphonic acid groups; and phosphinic acid groups.

[0040] Specific examples of the halogen-containing group include fluorine-containing groups such as PF6 and BF4, chlorine-containing groups such as ClO4 and SbCl6, and iodine-containing groups such as IO4. Specific examples of the heterocyclic compound residue include R 1 ~R 13 Examples of the above-mentioned examples include those similar to those given as examples.

[0041] Specific examples of the silicon-containing group include R 1 ~R 13 Specific examples of the silyl group include hydrocarbon-substituted silyl groups such as a phenylsilyl group, a diphenylsilyl group, a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tricyclohexylsilyl group, a triphenylsilyl group, a methyldiphenylsilyl group, a tritolylsilyl group, and a trinaphthylsilyl group; hydrocarbon-substituted silyl ether groups such as a trimethylsilyl ether group; silicon-substituted alkyl groups such as a trimethylsilylmethyl group; and silicon-substituted aryl groups such as a trimethylsilylphenyl group.

[0042] Specific examples of the germanium-containing group include R 1 ~R 13 Specifically, the silicon-containing group may be substituted with germanium.

[0043] Specific examples of the tin-containing group include R 1 ~R 13 Specific examples include groups in which silicon in the silicon-containing groups is substituted with tin. Of these, X is preferably a halogen atom or a hydrocarbon group.

[0044] In general formula (1), n ​​represents the valence of M, and specifically, is the same number as the valence of M. n is usually an integer of 3 to 7, preferably an integer of 3 to 6, more preferably 3 or 4, and particularly preferably 4. When n is 4 or more, the multiple Xs may be the same or different, and two or more of them may be linked together to form a ring.

[0045] In the present invention, a compound in which the presence or absence of a bond between Y and M in general formula (1) is not clear is also considered to be a transition metal compound (A) represented by general formula (1). Preferable specific examples of the transition metal compound (A) represented by general formula (1) are shown below.

[0046] [ka] In the above examples, Ad represents an adamantyl group, and Ph represents a phenyl group. In the above examples, preferred examples of the transition metal compound (A) include transition metal compounds in which titanium atoms are replaced with zirconium atoms or hafnium atoms.

[0047] (Method for producing transition metal compound (A)) The method for producing such a transition metal compound (A) is not particularly limited, and it can be produced, for example, as follows.

[0048] First, the ligand constituting the transition metal compound (A) can be produced, for example, by the following synthesis method, more specifically, by utilizing a reaction of coupling two or more materials. One example is a method in which a boronic acid derived from a phenol with a protected hydroxyl group is used as the raw material for the oxygen-containing site, and a halogenated ether with a nitro group is used as the raw material for the nitrogen-containing site, followed by Suzuki-Miyaura coupling reaction, followed by reductive amination of the nitro group of the obtained compound, and deprotection of the hydroxyl group.

[0049] The Suzuki-Miyaura coupling reaction between the boronic acid derived from the phenol with a protected hydroxyl group and a halogenated ether having a nitro group is specifically carried out by adding the solvent 1 described below to a mixture of these compounds, a basic compound, a palladium catalyst as a catalyst, and a compound that serves as a ligand for the palladium catalyst. The mixture may or may not be dissolved in the solvent 1, and the compound that serves as a ligand may or may not be added.

[0050] Examples of the basic compound include sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium tert-butoxide, potassium tert-butoxide, and tripotassium phosphate.

[0051] Specific examples of the palladium catalyst include bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tris(dibenzylideneacetone)(chloroform)dipalladium, palladium chloride, palladium acetate, dichlorobis(acetonitrile)palladium, dichlorobis(benzonitrile)palladium, allylpalladium chloride dimer, and the like.

[0052] Specific 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, as well as salts of phosphine compounds such as di-tert-butyl(methyl)phosphonium tetrafluoroborate.

[0053] In addition, a complex compound of the above-mentioned phosphine compound with palladium, such as dichlorobis(tricyclohexylphosphine)palladium, or a complex compound of a carbene type compound with palladium, such as {1,3-bis(2,6-diisopropylphenyl)imidazolidene}(3-chloropyridyl)palladium dichloride, may be used as a catalyst.

[0054] As the solvent 1, any solvent generally used in such reactions can be used, among which polar solvents such as tetrahydrofuran (THF), dimethoxyethane, 1,4-dioxane, N,N-dimethylformamide (DMF), ethanol, propanol, etc., or hydrocarbon solvents such as toluene, xylene, etc. may be preferred. Furthermore, these solvents may be mixed with water to be used as the solvent 1, and the mixing ratio (mass ratio) of water / solvent is preferably 0 / 100 to 25 / 75.

[0055] Boronic acids derived from phenols with protected hydroxyl groups can be synthesized by lithiation with an alkyllithium reagent in solvent 2 described below, followed by addition of a boronic acid ester. Specific examples of alkyllithium reagents include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide, etc. Furthermore, N,N,N',N'-tetramethylethylenediamine (TMEDA), hexamethylphosphoric acid triamide (HMPA), etc. may be added as an activator, and these may be used in the amount of a solvent.

[0056] Specific examples of the boronic acid ester include trimethoxyboronic acid, triethoxyboronic acid, and triisopropoxyboronic acid. Specific examples of the solvent 2 include diethyl ether, tetrahydrofuran (THF), tert-butyl methyl ether (TBME), and cyclopentyl methyl ether (CPME).

[0057] The protection of the hydroxyl group of a phenol is carried out according to a conventional method. Examples of the protecting group include tert-butyl, trityl, benzyl, p-methoxybenzyl, methoxymethyl, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, triisopropylsilyl, methanesulfonyl, acetyl, pivaloyl, 2,2,2-trichloroethoxycarbonyl, and allyloxycarbonyl.

[0058] Phenols can be obtained as they are from commercial sources, but can also be synthesized by alkylation of phenols with alcohols or by the Suzuki-Miyaura coupling reaction of halogenated phenols with arylboronic acids.

[0059] Commercially available halogenated ethers with nitro groups can be used as they are, but in the case of synthesis, they can be obtained by electrophilic substitution reaction between 2-halogenated phenols and 2-halogenated nitrobenzenes. Specifically, 2-halogenated phenols, 2-halogenated nitrobenzenes, and a basic compound as a catalyst are added to solvent 3 and reacted.

[0060] Examples of the basic compound include sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium tert-butoxide, potassium tert-butoxide, and tripotassium phosphate.

[0061] Specific examples of the solvent 3 include N,N-dimethylformamide and dimethylsulfoxide. Commercially available 2-halogenated phenols can be used as they are, but when they are synthesized, halogenation of phenols is carried out according to a conventional method. Commercially available 2-halogenated nitrobenzenes can be used as they are, but when they are synthesized, halogenation of nitrobenzenes or nitration of halogenated benzenes is carried out according to a conventional method.

[0062] The protecting group is then removed with a deprotecting agent such as hydrochloric acid, p-toluenesulfonic acid, etc. to give the ligand. The ligand thus obtained is then reacted with MX n (M, X, and n are the same as M, X, and n in general formula (1), respectively.) The corresponding transition metal compound (A) can be synthesized by reacting the ligand with a transition metal M-containing compound represented by the formula (A). Specifically, the synthesized ligand is dissolved in a solvent, and if necessary, contacted with a base to prepare an anion, and then mixed with a transition metal M-containing compound such as a metal halide, a metal alkylate, or a metal amide at a low temperature and stirred at -78°C to room temperature or under reflux conditions for about 1 to 48 hours. As the solvent, a solvent generally used in such a reaction can be used, and among them, polar solvents such as diethyl ether and tetrahydrofuran (THF), hydrocarbon solvents such as toluene, and dichloromethane are preferably used. In addition, examples of the base used in preparing the anion include metal salts such as lithium salts such as n-butyl lithium, sodium salts such as sodium hydride, triethylamine, pyridine, and the like.

[0063] 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 going through the preparation of the anion. Furthermore, the metal M in the synthesized transition metal compound (A) can be exchanged with another transition metal by a conventional method. 1 ~R 13 When one or more of is hydrogen, a substituent other than hydrogen can be introduced at any stage in the synthesis.

[0064] Furthermore, without isolating the transition metal compound, the reaction solution of the ligand and the metal compound can be used as it is for the production of an olefin polymerization catalyst described below.

[0065] <Olefin polymerization catalyst> The olefin polymerization catalyst of the present invention is a catalyst containing the transition metal compound (A) represented by the general formula (1) explained above. This catalyst preferably further contains (B) at least one compound selected from the group consisting of organometallic compounds (B-1), organoaluminum oxy compounds (B-2) and compounds (B-3) that react with the transition metal compound (A) to form an ion pair. In the present invention, the term "olefin" refers to a hydrocarbon having one carbon-carbon double bond in the molecule. The compound (B) will be described in detail below.

[0066] [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 (B) 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. Compounds (B-1), (B-2), and (B-3) are described below.

[0067] ((B-1) Organometallic compound) Specific examples of the organometallic compound (B-1) include organometallic compounds represented by the following general formulas (B-1a), (B-1b) and (B-1c). R a p Al(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 represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Y represents 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 represents Li, Na or K, and R c represents 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 represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. M 4 is Mg, Zn or Cd.)

[0068] Examples of the organoaluminum compound represented by general formula (B-1a) include the following compounds. R a p Al(OR b ) 3-p (In the formula, R a and R b may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. p is preferably a number such that 1.5 ≤ p ≤ 3.) The organoaluminum compound represented by R a p AlY 3-p (In the formula, Ra represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is preferably a number where 0 < p < 3.) an organoaluminum compound represented by R a p AlH 3-p (In the formula, R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number where 2 ≤ p < 3.) an organoaluminum compound represented by 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, represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, p is a number where 0 < p ≤ 3, q is a number where 0 ≤ q < 3, s is a number where 0 ≤ s < 3, and p + q + s = 3.) an organoaluminum compound represented by

[0069] More specifically, as the organoaluminum compound represented by the general formula (B-1a), tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, 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, tri-2-ethylhexylaluminum; Tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; Triarylaluminum 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); Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, and isobutyl aluminum isopropoxide; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide; Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide, butyl aluminum sesquibutoxide; R a 2.5 Al(OR b ) 0.5 (In the formula, R a and R b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms; dialkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), and isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide); Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride; Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide; partially halogenated alkylaluminums, such as alkylaluminum dihalides, such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, and the like; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Other partially hydrogenated alkylaluminums, such as alkylaluminum dihydrides, such as ethylaluminum dihydride, propylaluminum dihydride, etc.; Partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide Some examples include:

[0070] Compounds similar to the compound represented by (B-1a) can also be used as the organometallic compound (B-1), and examples of such compounds include organoaluminum compounds in which two or more aluminum compounds are bonded via nitrogen atoms.Specific examples of such compounds include (C2H5)2AlN(C2H5)Al(C2H5)2.

[0071] The compound represented by the general formula (B-1b) is LiAl(C2H5)4, LiAl(C7H 15 )4 can be mentioned as examples. Examples of the compound represented by general formula (B-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium, dimethylzinc, diethylzinc, diphenylzinc, di-n-propylzinc, diisopropylzinc, di-n-butylzinc, diisobutylzinc, bis(pentafluorophenyl)zinc, dimethylcadmium, and diethylcadmium.

[0072] 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.

[0073] Furthermore, a compound which 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). The organometallic compounds (B-1) as described above may be used singly or in combination of two or more kinds.

[0074] ((B-2) Organoaluminum oxy compound) The organoaluminum oxy compound (B-2) may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. Specific examples of the organoaluminum oxy compound (B-2) include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.

[0075] 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 the 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.

[0076] 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.

[0077] Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound represented by the general formula (B-1a) above.

[0078] Of these, trialkylaluminum and tricycloalkylaluminum are preferred, with trimethylaluminum being particularly preferred. The above organoaluminum compounds may be used singly or in combination of two or more.

[0079] Examples of the solvent used in the preparation of 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 halides of the aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially chlorides and bromides. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

[0080] 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 atom, i.e., it is preferably insoluble or poorly soluble in benzene.

[0081] The organoaluminum oxy compound (B-2) may also include boron-containing organoaluminum oxy compounds represented by the following general formula (3).

[0082] [ka] (In general formula (3), R 15 represents a hydrocarbon group having 1 to 10 carbon atoms, and four R 16 may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.)

[0083] The boron-containing organoaluminum oxy compound represented by the general formula (3) can be produced by reacting an alkylboronic acid represented by the following general formula (4) 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. R 17 -B(OH)2···(4) (In general formula (4), R 17 is R in the above general formula (3). 15 It shows the same group as

[0084] Specific examples of the alkylboronic acid represented by the above general formula (4) 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, 3,5-bis(trifluoromethyl)phenylboronic acid, etc. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These are used alone or in combination of two or more.

[0085] Specific 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.

[0086] The organoaluminum compound is preferably a trialkylaluminum or a tricycloalkylaluminum, more preferably a trimethylaluminum, a triethylaluminum or a triisobutylaluminum, which may be used alone or in combination of two or more. The above organoaluminum oxy compounds (B-2) may be used singly or in combination of two or more.

[0087] ((B-3) A compound that reacts with a transition metal compound (A) to form an ion pair) Examples of the compound (B-3) (hereinafter referred to as "ionized 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 JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and U.S. Patent No. 5,321,106. Further examples include heteropoly compounds and isopoly compounds.

[0088] Specifically, the Lewis acid includes 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), such as 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. The ionic compound may, for example, be a compound represented by the following general formula (5).

[0089] [ka] (In general formula (5), R 18 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 19 ~R 22 may be the same or different and are organic groups, preferably aryl groups or substituted aryl groups.

[0090] Specific examples of the carbonium cation include tri-substituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0091] Specific 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.

[0092] Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0093] R 18 As the cation, a carbonium cation and an ammonium cation are preferred, and in particular, a triphenylcarbonium cation, an N,N-dimethylanilinium cation, and an N,N-diethylanilinium cation are preferred.

[0094] Further, examples of the ionic compound include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0095] Specific examples of the trialkyl-substituted ammonium salt 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.

[0096] Specific 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.

[0097] Specific examples of the dialkylammonium salt include di(1-propyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, and the like.

[0098] 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 (6) or (7).

[0099] [ka] (In formula (6), Et represents an ethyl group.)

[0100] [ka] (In formula (7), Et represents an ethyl group.)

[0101] Specific examples of the borane compounds that are examples of the ionizable ionic compound (B-3) include decaborane (14); 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; Salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydride dodecaborate)cobaltate(III) and bis[tri(n-butyl)ammonium]bis(dodecahydride dodecaborate)nickelate(III). etc.

[0102] Specific examples of carborane compounds that are examples of the ionized ionic compound (B-3) include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane (13), 2,7-dicarbaundecaborane (13), undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane (13), 2,7-dicarbaundecaborane (13), and undecahydride-1,3-dimethyl-1,3-dicarbanonaborane. Hydride-7,8-dimethyl-7,8-dicarboxedecaborane, dodecahydride-11-methyl-2,7-dicarboxedecaborane, 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 ammonium 6-carbadecaborate (14), tri(n-butyl)ammonium 6-carbadecaborate (12), tri(n-butyl)ammonium 7-carbaundecaborate (13), tri(n-butyl)ammonium 7,8-dicarboxaundecaborate (12), tri(n-butyl)ammonium 2,9-dicarboxaundecaborate (12), tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarboxaundecaborate, tri(n-butyl)ammonium undecahydride-8- Salts of anions such as ethyl-7,9-dicarboxadecaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarboxadecaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboxadecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboxadecaborate, 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-dicarbandecaborate)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) Salts of metal carborane anions such as tri(n-butyl)ammonium bis(undecahydride-7-carboudecaborate)ferrate(III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboxaborate)chromate(III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboxaborate)cobaltate(III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carboudecaborate)chromate(III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboudecaborate)manganate(IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboudecaborate)cobaltate(III), and bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboudecaborate)nickelate(IV). etc.

[0103] A heteropoly compound, which is an example of the ionizing ionic compound (B-3), is a compound containing an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. Specific examples of the acid include, but are not limited to, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanomolybdic acid, germanomolybdic acid, arsenic molybdic acid, tinmolybdic 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.

[0104] The isopoly compound, which is an example of the ionized ionic compound (B-3), is a compound composed of a metal ion of one type of atom selected from vanadium, niobium, molybdenum, and tungsten, and can be considered to be a molecular ion species of metal oxide.Specific examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids.In addition, examples of the salts include salts of the acids with metals of Group 1 or Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.

[0105] The above-mentioned ionizing ionic compound (compound (B-3) which reacts with the transition metal compound (A) to form an ion pair) may be used alone or in combination of two or more kinds. When an organoaluminum oxy compound (B-2) such as methylaluminoxane is used as a cocatalyst component in addition to the transition metal compound (A), extremely high polymerization activity for olefin compounds is exhibited.

[0106] The olefin polymerization catalyst according to the present invention may contain the transition metal compound (A) and at least one compound (B) selected from the group consisting of organometallic compounds (B-1), organoaluminum oxy compounds (B-2), and ionizing ionic compounds (B-3), and may also contain the following support (C) as necessary.

[0107] [Carrier (C)] The carrier (C) is an inorganic or organic compound, and is a granular or fine particle solid. By supporting the transition metal compound (A) and the compound (B) on the carrier (C), a polymer with good morphology can be obtained.

[0108] The inorganic compound is preferably a porous oxide, an inorganic halide, a clay, a clay mineral, or an ion-exchangeable layered compound. Specifically, the porous oxide may be SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, or a composite or mixture containing these, and may further be, for example, natural or synthetic zeolite, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc. Among these, the porous oxide is preferably one having SiO2 and / or Al2O3 as the main component.

[0109] In addition, 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.

[0110] The properties of such porous oxides vary depending on the type and production 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 0.3-3.0 cm 3 / g range. Such a porous oxide is calcined at 100 to 1000°C, preferably 150 to 700°C, as required, before use.

[0111] As the inorganic halide, MgCl2, MgBr2, MnCl2, MnBr2, etc. can be used. The inorganic halide can be used as it is, or can be used after being pulverized by a ball mill or a vibration mill. In addition, the inorganic halide can be dissolved in a solvent such as alcohol, and then precipitated into fine particles by a precipitating agent.

[0112] The clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which the planes formed by ionic bonds are stacked in parallel with each other with weak bonding force, and the ions contained therein are exchangeable. Most clay minerals are ion-exchangeable layered compounds. The clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products, and artificial synthetic products can also be used.

[0113] Examples of the clay, clay mineral, or ion-exchangeable layered compound include ionic crystalline compounds having layered crystal structures such as hexagonal close packing type, antimony type, CdCl2 type, and CdI2 type.

[0114] Furthermore, examples of clay and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, halloysite, etc. Examples of ion-exchangeable layered compounds include crystalline acid salts of polyvalent metals such as α-Zr(HAsO4)2·H2O, α-Zr(HPO4)2, α-Zr(KPO4)2·3H2O, α-Ti(HPO4)2, α-Ti(HAsO4)2·H2O, α-Sn(HPO4)2·H2O, γ-Zr(HPO4)2, γ-Ti(HPO4)2, and γ-Ti(NH4PO4)2·H2O.

[0115] Such clay, clay mineral, or ion-exchangeable layered compound preferably has 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, where the pore volume is measured for a pore radius range of 20 to 30,000 Å by mercury intrusion porosimetry using a mercury porosimeter.

[0116] When a support having a pore volume of less than 0.1 cc / g and a radius of 20 Å or more is used, it tends to be difficult to obtain high polymerization activity. It is also preferable to subject the clay and clay minerals to chemical treatment. As the chemical treatment, any of surface treatments that remove impurities adhering to the surface and treatments that affect the crystalline structure of the clay can be used. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment. In addition to removing impurities from the surface, acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystalline structure. In alkali treatment, the crystalline structure of the clay is destroyed, resulting in a change in the structure of the clay. In addition, salt treatment and organic treatment form ion complexes, molecular complexes, organic derivatives, etc., which can change the surface area and interlayer distance.

[0117] The ion-exchangeable layered compound may be a layered compound in which the space between layers is expanded by utilizing the ion exchangeability and exchanging the exchangeable ions between layers with other large bulky ions. Such bulky ions play a role of supporting the layered structure and are usually called pillars. The introduction of another substance between layers of a layered compound in this way 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 (R is a hydrocarbon group, etc.), [Al 13 O4(OH) 24 ] 7+ , [Zr4(OH) 14 ] 2+ , [Fe3O(OCOCH3)6] + Metal hydroxide ions such as these can be used. These compounds can be used alone or in combination of two or more. When these compounds are intercalated, polymers obtained by hydrolysis of metal alkoxides (R represents a hydrocarbon group, etc.) such as Si(OR)4, Al(OR)3, Ge(OR)4, etc., and colloidal inorganic compounds such as SiO2 can also be coexisted. Examples of pillars include oxides generated by intercalating the metal hydroxide ions between layers and then dehydrating them with heat.

[0118] The clay, clay mineral, and ion-exchangeable layered compound may be used as is, or after treatment such as ball milling or sieving. They may also be used after adding and adsorbing new water or after heat dehydration treatment. Furthermore, these may be used alone or in combination of two or more.

[0119] Of these, clay or clay minerals are preferred, and montmorillonite, vermiculite, pectolite, taeniolite and synthetic mica are particularly preferred. As described above, the carrier (C) is an inorganic or organic compound, and examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm.Specific examples include (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or (co)polymers produced mainly from vinylcyclohexane and styrene, and their modified products.

[0120] The olefin polymerization catalyst according to the present invention contains the transition metal compound (A), preferably the compound (B), and, if necessary, a support (C). In addition to these, if necessary, the catalyst may further contain the following specific organic compound component (D).

[0121] [Organic compound component (D)] In the present invention, the organic compound component (D) is used, if necessary, for the purpose of improving the polymerization performance (e.g., catalytic activity) of the olefin polymerization catalyst of the present invention and the physical properties of the produced polymer (e.g., increasing the molecular weight of the produced polymer). Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, organic phosphorus compounds, and sulfonic acids.

[0122] The alcohols and phenolic compounds are generally selected from the group consisting of R 23 -OH, where R 23 represents 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).

[0123] Alcohols include R 23 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.

[0124] The carboxylic acid is usually R 24The one represented by -COOH is used. 24 represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and is particularly preferably a halogenated hydrocarbon group having 1 to 50 carbon atoms.

[0125] As the organic phosphorus compound, phosphoric acids having a POH bond, phosphates having a P-OR or P=O bond, and phosphine oxide compounds are preferably used. The sulfonic acids include those represented by the following general formula (8).

[0126] [ka] (In general formula (8), M 2 is an element in groups 1 to 14 of the periodic table, R 25 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms; t is M 2 is the valence of tu is an integer greater than or equal to 0.)

[0127] In the above formula (8), M 2 is preferably an element of Groups 2 to 14 of the periodic table. 2 is preferably a metal element. The sulfonic acids are preferably sulfonates. The organic compound components may be used alone or in combination of two or more.

[0128] <Method of producing olefin polymer> The method for producing an olefin polymer of the present invention is a method for homopolymerizing or copolymerizing an olefin in the presence of the above-described olefin polymerization catalyst. As described above, in the present invention, an olefin refers to a hydrocarbon having one carbon-carbon double bond in the molecule. In the present invention, the copolymerization of an olefin may be performed as long as 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.

[0129] In the polymerization, the components constituting the catalyst of the present invention may be used in any manner and added in any order to a polymerization vessel. Examples of the manner include the following. (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 catalyst component comprising a transition metal compound (A) and a compound (B) 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 compound (B) are added to a polymerization vessel 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 the catalyst component in which the compound (B) is supported on the carrier (C), the transition metal compound (A), and the compound (B) are added to a polymerization vessel 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 vessel 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) which have been 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) are previously contacted, the compound (B), and an organic compound component (D) are added to a polymerization vessel in any order. In this case, the compounds (B) may be the same or different. (16) A method of adding a catalyst component in which a transition metal compound (A) is contacted with a compound (B) in advance, and a component in which a compound (B) is contacted with an organic compound component (D) in advance, to a polymerization vessel 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 with each other are added to a polymerization reactor in any order. (19) A method in which a catalyst component prepared 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 vessel. (20) A method in which a catalyst component in which a transition metal compound (A), a compound (B) and an organic compound component (D) are contacted in advance in any order, and the compound (B) are added to a polymerization vessel in any order. In this case, the compounds (B) may be the same or different. (21) A method in which a catalyst comprising a transition metal compound (A), a compound (B) and an organic compound component (D) 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 vessel in any order. In this case, the compounds (B) may be the same or different.

[0130] In the above-mentioned solid catalyst component having the transition metal compound (A) supported on the support (C) and the solid catalyst component having the transition metal compound (A) and the compound (B) supported on the support (C), an olefin may be prepolymerized, or a further catalyst component may be supported on the prepolymerized solid catalyst component.

[0131] In the present invention, polymerization can be carried out by either liquid phase polymerization such as solution polymerization or suspension polymerization, or gas phase polymerization.Specific examples of the inert hydrocarbon medium used in the 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, and the olefin (monomer) itself to be subjected to (co)polymerization can also be used as a solvent.

[0132] 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 -12 ~1×10 -2 Molar, preferably 1 x 10 -10 ~1×10 -3 It is used in molar amounts.

[0133] The organometallic compound (B-1) is used in an amount such that the molar ratio [(B-1) / M] of the organometallic compound (B-1) to the total transition metal atoms (M) in the transition metal compound (A) is usually 0.01-100,000, preferably 0.05-50,000. The organoaluminum oxy compound (B-2) is used in an amount such that the molar ratio [(B-2) / M] of the aluminum atoms in the organoaluminum oxy compound (B-2) to the total transition metals (M) in the transition metal compound (A) is usually 10-500,000, preferably 20-100,000. The compound (ionized 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 [(B-3) / M] of the ionized ionic compound (B-3) to the transition metal atoms (M) in the transition metal compound (A) is usually 1-10, preferably 1-5.

[0134] When the support (C) is used, it is used in an amount such that the weight ratio of the transition metal compound (A) to the support (C) [(A) / (C)] is preferably 0.0001 to 1, more preferably 0.0005 to 0.5, and even more preferably 0.001 to 0.1.

[0135] When the compound (B) is an organometallic compound (B-1), the organic compound component (D) is used in an amount such that the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0.1 to 5. When the compound (B) is an organoaluminum oxy compound (B-2), the organic compound component (D) is used in an amount such that the molar ratio [(D) / (B-2)] is usually 0.001 to 2, preferably 0.005 to 1. When the compound (B) is an ionized ionic compound (B-3), the organic compound component (D) is used in an amount such that the molar ratio [(D) / (B-3)] is usually 0.01 to 10, preferably 0.1 to 5.

[0136] The polymerization temperature of the olefin using such an olefin polymerization catalyst is usually in the range of −50 to +200° C., preferably 0 to 170° C. The polymerization pressure is usually normal pressure to 100 kg / cm. 2 -G, preferably normal pressure to 50 kg / cm 2Under the conditions of -G, the polymerization reaction can be carried out in any of batch, semi-continuous and continuous modes. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

[0137] The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature, and can also be adjusted by the amount of compound (B) used.

[0138] When olefins are copolymerized in the presence of the olefin polymerization catalyst of the present invention, the difference in copolymerization reactivity of each olefin tends to be smaller than that in the past, although this depends on the type of olefins to be combined. Therefore, when olefins are copolymerized in the presence of the olefin polymerization catalyst of the present invention in industrially producing a copolymer, it is expected that process control will be simplified and that copolymers with a narrow composition distribution will be easily produced stably.

[0139] The reason for such characteristics is unclear at present, but the inventors have made several speculations as follows. The transition metal compound (A) has a structure in which one ligand coordinates to a metal atom via at least three heteroatoms. For this reason, the transition metal compound (A) is expected to have a stable structure with little fluctuation. One theory behind this is that the smaller the bulk of the olefin, the easier it is to coordinate to the heteroatom, which suppresses the polymerization rate and reduces the difference in polymerization rate with the bulkier olefin.

[0140] Furthermore, as described above, the transition metal compound (A) of the present invention is structurally stable and has little fluctuation, and is predicted from computational science to have a wide coordination space. Therefore, it is considered that the compound is less affected by the olefin structure, that is, even bulky olefins tend to easily approach the central metal (which is considered to be the active site).

[0141] In addition, although the analytical accuracy is not high at present, the polymer obtained by using the olefin polymerization catalyst of the present invention seems to have many heterogeneous bond structures. Conventionally, the polymerization rate may be extremely decreased in a reaction process in which a heterogeneous bond is formed. (The occurrence of this heterogeneous bond reaction is considered to be one of the reasons why the reaction rate of α-olefins (structures that can form heterogeneous bonds) having 3 or more carbon atoms is lower than that of ethylene (structures that do not form heterogeneous bonds).) The olefin polymerization catalyst containing the transition metal compound (A) of the present invention has the property that the polymerization rate does not decrease even when a heterogeneous bond reaction occurs, so there is also the idea that there is little difference in copolymerization reactivity.

[0142] Because of these characteristics, the olefin polymerization catalyst of the present invention can be used to easily produce copolymers of any composition. For example, when producing a polymer using two types of olefins, the composition ratio can be freely adjusted from 1 / 99 to 99 / 1 in molar ratio.

[0143] The olefins that can be polymerized using the olefin polymerization catalyst of the present invention are not particularly limited, but include linear or branched α-olefins having 2 to 30 carbon atoms, 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, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene. These olefins can be used alone or in combination of two or more. Among the above olefins, olefins having 2 to 20 carbon atoms are preferred, and olefins having 2 to 10 carbon atoms are more preferred.

[0144] In the method for producing an olefin-based polymer of the present invention, it is preferable to use an olefin having 2 to 10 carbon atoms as the essential component, it is more preferable to use an olefin selected from ethylene, propylene, and 1-butene as the essential component, it is even more preferable to use ethylene or propylene as the essential component, and it is particularly preferable to use an embodiment in which ethylene is the essential component.

[0145] In the method for producing an olefin polymer of the present invention, an olefin may be copolymerized 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).

[0146] Specific 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, and 19-eicosene. Acid, 20-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 bicyclo[2.2.1]-5-heptene-2-carboxylic acid and bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid, metal salts such as sodium salts, potassium salts, lithium salts, zinc salts, magnesium salts and calcium salts of these unsaturated carboxylic acids, 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, it may be a monoester or a diester), and unsaturated carboxylic acid amides such as amides of these unsaturated carboxylic acids and N,N-dimethylamides (when the unsaturated carboxylic acid is a dicarboxylic acid, it may be a monoamide or a diamide); 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 bromide; 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, 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; Unsaturated sulfones such as allyl phenyl sulfone; Unsaturated phosphines such as allyldiphenylphosphine; Unsaturated phosphine oxides such as allyldiphenylphosphine oxide etc.

[0147] Furthermore, examples of the polar group-containing monomer include vinylbenzyl acetate, hydroxystyrene, 4-(3-butenyloxy)methyl 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, allyl glycine, N-vinylpyrrolidone, allyltrichlorosilane, acryltrimethylsilane, allyldimethyl(diisopropylamino)silane, 7-octenyltrimethoxysilane, allyloxytrimethylsilane, and allyloxytriphenylsilane, which can be copolymerized with olefins in the presence of the olefin polymerization catalyst of the present invention.

[0148] In addition, as monomers other than the polar group-containing monomer, vinylcyclohexane, dienes, polyenes, etc. can be used. In the presence of the olefin polymerization catalyst of the present invention, these monomers can also be copolymerized with olefins.

[0149] The diene or polyene may be a cyclic or chain compound having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, and two or more carbon-carbon double bonds. Specific examples include 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, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene, divinylbenzene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene.

[0150] As further other monomers, aromatic vinyl compounds can be used, specifically, mono- or polyalkylstyrenes such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene; functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, and p-chlorostyrene; and 3-phenylpropylene, 4-phenylpropylene, and α-methylstyrene.

[0151] Depending on the type of monomer used, the combination may have a significantly different copolymerization reactivity. In such a case, the difference in copolymerization reactivity can be reduced by appropriately selecting the structure of the olefin polymerization catalyst depending on the type of monomer used.

[0152] According to the method for producing an olefin polymer of the present invention, it is possible to obtain an olefin polymer having a wide molecular weight range from low molecular weight to ultra-high molecular weight. As a specific example, it is possible to produce an olefin polymer having a weight average molecular weight of 1000 to 5 million. The lower limit of the weight average molecular weight is preferably 5,000, more preferably 10,000, and even more preferably 30,000. On the other hand, the upper limit is preferably 3 million, more preferably 2 million, and even more preferably 1 million.

[0153] As described above, the polymer produced by the method for producing an olefin polymer of the present invention may have many heterogeneous bonds. Furthermore, the formation of heterogeneous bonds has been considered to be disadvantageous in increasing the molecular weight. However, by using the method for producing an olefin polymer of the present invention, it may be possible to obtain a polymer having a high molecular weight even if it has many heterogeneous bonds.

[0154] The molecular weight of the olefin polymer produced by the method for producing a polymer of the present invention is determined by GPC measurement carried out under the conditions described in the Examples section below. According to the method for producing an olefin polymer of the present invention, as explained above, a polymer can be produced with high polymerization activity. In addition, there is little difference in copolymerization reactivity during copolymerization, and the method may exhibit advantageous characteristics for industrially obtaining a copolymer. For this reason, the present invention has great industrial value. Specifically, while the present invention can be suitably used in a continuous polymerization process, it can be said that the present invention has a great advantage, particularly for production in a batch polymerization process. EXAMPLES

[0155] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these. The structure of the compound obtained in the synthesis example is 270MHz 1 The determination was performed using H NMR (manufactured by JEOL, instrument name GSH-270), GC-MS (manufactured by Shimadzu Corporation, instrument name QP2010 Ultra), FD-mass spectrometry (manufactured by JEOL, instrument name SX-102A), etc.

[0156] The molecular weight of the polymer obtained in the examples was measured by gel permeation chromatography (manufactured by Waters, device name Alliance GPC2000 type) under the following operating conditions.

[0157] Measurement equipment: Gel permeation chromatograph Alliance GPC2000 (Waters) Analysis software: Chromatography data system Empower3 (trademark, Waters) Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 2 (both 7.5 mm inner diameter x 30 cm length, Tosoh Corporation) Mobile phase: o-Dichlorobenzene [=ODCB] (Wako Pure Chemical Industries, Ltd., special grade reagent) Detector: Differential refractometer (built into the device) Column temperature: 140°C Flow rate; 1.0mL / min Injection volume; 400μL Sampling time interval: 0.5 seconds Sample concentration: 0.15% (w / v) Molecular weight calibration: Monodisperse polystyrene (Tosoh Corporation) / molecular weight 495 to 20.6 million

[0158] The weight average molecular weight was calculated in terms of polyethylene molecular weight according to the general calibration procedure described in J. Polym. Sci. 1967, B5, 753. The propylene content of ethylene / propylene copolymer is 125MHz. 13 The measurements were performed using a C NMR (Bruker Biospin, AVANCEIIIcryo-500 instrument).

[0159] [Synthesis Example 1] In a 100 mL reactor that had been thoroughly dried and purged with nitrogen, 3.13 g (14.2 mmol) of 2-iodophenol, 1.0 mL (9.47 mmol) of 2-fluoronitrobenzene, 2.16 g (14.2 mmol) of cesium fluoride, 3.96 g (28.6 mmol) of potassium carbonate, and 14 mL of dimethyl sulfoxide were charged, and the mixture was stirred at 50°C for 6 hours. After cooling to room temperature, 20 mL of water was added to the reaction solution, and the soluble matter was extracted with dichloromethane. The obtained fraction was washed with 1 M aqueous sodium hydroxide solution and saturated saline, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was distilled under reduced pressure to remove the solvent. Thereafter, the filtrate was diluted with ethyl acetate, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was distilled under reduced pressure to remove the solvent, and 3.14 g (yield 97%) of the target product represented by the following formula (1) (hereinafter referred to as compound (1)) was obtained.

[0160] GC-Mass spectrometry (M+):341 1 H-NMR(270MHz,CDCl3):8.00(1H,dd,J=8.4,1.6Hz),7.91(1H,dd,J=7.8,1.4Hz),7.50(1H,ddd,J=8.1,7.6,1.6Hz),7.35(1H,ddd,J=8 ppm

[0161] [ka]

[0162] [Synthesis Example 2] In a 300mL reactor that had been thoroughly dried and purged with nitrogen, 10.3g (50.0mmol) of 2,4-di-t-butylphenol and 75mL of tetrahydrofuran were charged and cooled to 0°C. 2.83g (60wt%, 70.7mmol) of sodium hydride (oil-based) was added and stirred at 0°C for 1 hour, and then 5.2mL (68.5mmol) of chloromethyl methyl ether was added at 0°C. After stirring at room temperature for 16 hours, water was added little by little under ice cooling to quench the reaction. The soluble matter was extracted with ethyl acetate, and the obtained fraction was washed with saturated saline and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was distilled under reduced pressure to obtain a light brown solid. The solid obtained here was charged in a 200mL reactor that had been thoroughly dried and purged with nitrogen, and 55mL of diethyl ether was added to dissolve it. 18mL (29.5mmol) of n-butyllithium hexane solution was added to this solution. After stirring at room temperature for 3 hours, the mixture was cooled to -78°C, 3.2mL (28.7mmol) of trimethoxyborane was added, and the mixture was stirred while gradually raising the temperature to room temperature. After 16 hours, the reaction solution was distilled under reduced pressure to remove the solvent, and thoroughly dried under reduced pressure to obtain a white solid. Compound (1) 6.83g (20.0mmol), palladium acetate 0.23g (1.01mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl 0.82g (2.01mmol), potassium phosphate 12.8g (60.2mmol), tetrahydrofuran 34mL, and water 8.5mL were charged, and the mixture was heated at 60°C in an oil bath for 6 hours. After cooling the reaction solution to room temperature, ethyl acetate was added, and the mixture was filtered through Celite. The filtrate was diluted with ethyl acetate, washed with water and saturated saline, and dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the filtrate was distilled off the solvent under reduced pressure to obtain a residue, which was purified by silica gel column chromatography to obtain 8.00 g (yield 86%) of the target substance represented by the following formula (2) (hereinafter referred to as compound (2)).

[0163] GC-Mass spectrometry (M+):463 1H-NMR(270MHz, CDCl3):7.87(1H,dd,J=8.4,1.6Hz),7.50(1H,dd,J=7.6,1.9Hz),7.46- 7.22(4H,m),7.12-6.97(4H,m),4.58(2H,s),3.25(3H,s),1.41(9H,s),1.21(9H,s)ppm

[0164] [ka]

[0165] [Synthesis Example 3] In a 300mL reactor that had been thoroughly dried and purged with nitrogen, 7.99g (17.2mmol) of compound (2), 1.29g (10wt%, 1.22mmol) of palladium carbon, 3mL of acetic acid, and 57mL of ethanol were charged and stirred at room temperature under a hydrogen atmosphere. After 8 hours, the reactor was purged with nitrogen, and the reaction solution was filtered through Celite. The obtained filtrate was diluted with ethyl acetate, washed with an aqueous sodium bicarbonate solution and saturated saline, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was distilled under reduced pressure to obtain 7.41g of a light brown amorphous body. 6.58g (15.2mmol) of the obtained amorphous body was placed in a 500mL reactor, and 6.90g (38.0mmol) of copper acetate (II), 4.3mL (53.4mmol), and 1,4-dioxane 187mL were further added and stirred at room temperature. After 15 minutes, 2.28 g (38.0 mmol) of methylboronic acid was added and stirred at 100° C. After 6 hours, the mixture was cooled to room temperature, filtered through Celite, and the residue obtained by distilling off the solvent from the filtrate under reduced pressure was purified by silica gel column chromatography to obtain 4.75 g (yield 69%) of the target product represented by the following formula (3) (hereinafter referred to as compound (3)).

[0166] GC-Mass Spectrometry (M+): 447 1H-NMR(270MHz,CDCl3):7.39(1H,dd,J=7.3,1.6Hz),7.37(1H,d,J=2.4Hz),7.26-7.21(1H, m),7.19(1H,d,J=2.7Hz),7.09(1H,dd,J=7.3,1.4Hz),7.07-7.01(1H,m),6.85(2H,dt,J=8 .3,1.4Hz),6.66(1H,dd,J=8.1,1.6Hz),6.59(1H,dt,J=7.6,1.6Hz),5.07(1H,d,J=5.1Hz) ,4.69(1H,s),4.49(1H,s),3.15(3H,s),2.80(3H,d,J=5.1Hz),1.47(9H,s),1.31(9H,s)ppm

[0167] [ka]

[0168] [Synthesis Example 4] In a thoroughly dried 200 mL reactor, 4.75 g (10.6 mmol) of compound (3), 6.06 g (31.9 mmol) of paratoluenesulfonic acid monohydrate, 75 mL of ethanol, and 15 mL of dichloromethane were charged and stirred at 50° C. for 4 hours. The reaction solution was cooled to room temperature, and the solvent was distilled off under reduced pressure. After dilution with dichloromethane, the solution was washed with an aqueous sodium bicarbonate solution and saturated saline, and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was distilled off under reduced pressure to obtain 4.24 g (yield 99%) of the target product represented by the following formula (4) (hereinafter referred to as compound (4)).

[0169] GC-Mass Spectrometry: 403 1H-NMR(270MHz,CDCl3):7.40(1H,dd,J=7.6,1.6Hz),7.35-7.27(1H,m),7.32(1H,d, J=2.4Hz),7.18(1H,dt,J=7.6,1.4Hz),7.09(1H,d,J=1.4Hz),7.07-7.00(1H,m),6.9 6(1H,dd,J=8.1,1.1Hz),6.85(1H,dd,J=8.1,1.1Hz),6.63(1H,dd,J=7.6,1.6Hz),6. 64-6.58(1H,m),5.33(1H,s),4.24(1H,s),2.74(3H,s),1.44(9H,s),1.30(9H,s)ppm

[0170] [ka]

[0171] [Example A1] In a 100mL reaction vessel that had been thoroughly dried and purged with nitrogen, 0.13g (60wt%, 3.30mmol) of sodium hydride (oil-based) was placed, and 20mL of a tetrahydrofuran solution containing 0.40g (0.99mmol) of compound (4) obtained in Synthesis Example 4 was added dropwise over 10 minutes, and the mixture was stirred at room temperature for 4 hours. The reaction solution was cooled to -78°C with dry ice-acetone, and 0.99mL (1M toluene solution, 0.99mmol) of titanium tetrachloride was added. The mixture was then stirred for 16 hours while slowly returning to room temperature. The solvent of the reaction solution was distilled off, 20mL of methylene chloride was added to the residue, and the mixture was stirred for a while, after which the insoluble matter was removed with a glass filter, and the filtrate was concentrated to about 1 / 3. 30 mL of n-hexane was added thereto and the mixture was concentrated to about 1 / 3. Insoluble matter was then filtered off using a glass filter, and the resulting solid was washed with 15 mL of n-hexane and dried under reduced pressure to obtain 0.23 g (45% yield) of the target compound represented by the following formula (A) (hereinafter referred to as titanium compound (A)). FD-Mass Spectrometry (M + ):519

[0172] [ka]

[0173] [Example B1] 250 ml of toluene was charged into a 500 ml glass reactor that had been thoroughly purged with nitrogen, and the liquid and gas phases were saturated with ethylene (supplied at 100 liters / hr). Then, 0.125 mmol of triisobutylaluminum (TIBA) was added, followed by 0.001 mmol of the titanium compound (A) obtained in Example A1 and 0.003 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate (TrB) to initiate polymerization. Ethylene was continuously supplied at 100 liters / hr, and polymerization was carried out for 5 minutes at normal pressure and 25°C, after which a small amount of isobutanol was added to terminate the polymerization.

[0174] After the polymerization was completed, the reaction mixture was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with methanol, the mixture was dried under reduced pressure at 80°C for 10 hours to obtain 0.51 g of polyethylene. The polymerization activity was 6120 kg / mol-Ti·hr, and the weight-average molecular weight (M w ) was 660,000.

[0175] [Example B2] 250 ml of toluene was charged into a 500 ml glass reactor that had been thoroughly purged with nitrogen, and the liquid and gas phases were saturated with ethylene (supplied at 50 L / hr) and propylene (supplied at 150 L / hr). Then, 0.125 mmol of triisobutylaluminum (TIBA) was added, followed by 0.005 mmol of the titanium compound (A) obtained in Example A1 and 0.015 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate (TrB) to initiate polymerization. Ethylene was continuously supplied at 50 L / hr and propylene at 150 L / hr, and polymerization was carried out at normal pressure for 10 minutes at 50°C, after which a small amount of isobutanol was added to terminate the polymerization.

[0176] After the polymerization was completed, the reactant was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with methanol, it was dried under reduced pressure at 130°C for 10 hours to obtain 3.83 g of ethylene / propylene copolymer. The polymerization activity was 4596 kg / mol-Ti·hr, and the propylene content of the obtained copolymer was 69.5 mol%, and the weight average molecular weight (M w ) was 260,000.

[0177] [Example B3] 250 ml of toluene was charged into a 500 ml glass reactor that had been thoroughly purged with nitrogen, and the liquid and gas phases were saturated with ethylene (supplied at 100 L / hr) and propylene (supplied at 100 L / hr). Then, 0.125 mmol of triisobutylaluminum (TIBA) was added, followed by 0.005 mmol of the titanium compound (A) obtained in Example A1 and 0.015 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate (TrB) to initiate polymerization. Ethylene was continuously supplied at 100 L / hr and propylene was continuously supplied at 100 L / hr, and polymerization was carried out at normal pressure and 50°C for 10 minutes, after which a small amount of isobutanol was added to terminate the polymerization.

[0178] After the polymerization was completed, the reactant was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with methanol, it was dried under reduced pressure at 130°C for 10 hours to obtain 3.68 g of ethylene / propylene copolymer. The polymerization activity was 4416 kg / mol-Ti·hr, and the propylene content of the obtained copolymer was 50.3 mol%, and the weight average molecular weight (M w ) was 510,000. [Industrial Applicability]

[0179] The olefin polymerization catalyst containing the novel transition metal compound of the present invention exhibits high olefin polymerization activity and excellent copolymerization reactivity, and therefore the present invention is of extremely high industrial value.

Claims

1. A transition metal compound (A) represented by the following general formula (1): 【Chemistry 1】 (In general formula (1), M represents a transition metal atom of Groups 3 to 10 of the periodic table. R 1 ~R 13 may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group; R 1 ~R 13 Two or more of these may be linked to each other to form a ring, and the ring may further have the above-mentioned substituent. Y is an oxygen atom, a sulfur atom, or -N(-R 14 )-(R 14 represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. The straight lines at the left and right ends represent bonds between a nitrogen atom and an adjacent carbon atom. ). n indicates the valence of M. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when a plurality of Xs are present, they may be the same or different, and two or more Xs may be linked together to form a ring.

2. 2. The transition metal compound (A) according to claim 1, wherein in the general formula (1), M is a transition metal atom of Group 4 of the periodic table, and n is 4.

3. The transition metal compound (A) according to claim 1, wherein Y in the general formula (1) is an oxygen atom.

4. An olefin polymerization catalyst comprising the transition metal compound (A) according to any one of claims 1 to 3.

5. (B) (B-1) Organometallic compound (B-2) an organoaluminum oxy compound, and (B-3) A compound that reacts with the transition metal compound (A) to form an ion pair The olefin polymerization catalyst according to claim 4, further comprising at least one compound selected from the group consisting of:

6. A process for producing an olefin polymer, comprising homopolymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 4.

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