Polymerization methods for olefins

Abstract

To provide a method for polymerizing olefins by using a catalyst containing a transition metal compound and an organoaluminum oxy compound to generate a high molecular weight olefin polymer with high polymerization activity.SOLUTION: The present invention relates to a method for polymerizing olefins, comprising: Step (α) of obtaining an olefin polymerization catalyst by contacting a transition metal compound (A) and a liquid organoaluminum oxy compound (B) under the following condition (α1); and then Step (β) of contacting the olefin polymerization catalyst and an olefin(s). (α1) An Al atom converted concentration of the organoaluminum oxy compound (B) in Step (α) is 0.004 to 0.5 mol / l.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for polymerizing olefins, and more particularly to a method for polymerizing olefins using a transition metal compound and an organoaluminum oxy compound.

Background Art

[0002] As catalysts for producing olefin polymers such as ethylene polymers and ethylene-α-olefin copolymers, titanium-based catalysts composed of titanium compounds and organoaluminum compounds, and vanadium-based catalysts composed of vanadium compounds and organoaluminum compounds are known. In addition, so-called metallocene catalysts composed of metallocene compounds such as zirconocene and organoaluminum oxy compounds (also referred to as aluminoxanes or alumoxanes) are known as catalysts capable of producing olefin polymers with high polymerization activity. Furthermore, a catalyst composed of at least one compound selected from a transition metal complex containing a nitrogen atom or an oxygen atom in the ligand, which is called a post-metallocene catalyst, an organometallic compound, an organoaluminum oxy compound, and a compound that reacts with the transition metal complex to form an ion pair, has been disclosed to be a powerful catalyst showing extremely high polymerization activity and specific reactivity (for example, Patent Document 1).

[0003] However, although such post-metallocene catalysts exhibit high activity, the molecular weight of the polymer produced may be low. On the other hand, it has also been found that when the above transition metal complex, organometallic compound, and compound that reacts with the transition metal complex to form an ion pair are brought into contact in a state where substantially no olefin is present, and then the olefin polymerization catalyst and olefin are brought into contact, an olefin polymer with high molecular weight can be obtained with high polymerization activity (for example, Patent Document 2).

[0004] In the manufacturing process of olefin polymers, it is preferable to use solid catalysts, such as slurry polymerization and gas-phase polymerization. However, in such cases, compounds that react with the aforementioned transition metal complexes to form ion pairs may have limitations in their use as supported catalysts. On the other hand, organoaluminum oxy compounds can be supported on carriers such as silica, and supported solid catalysts using this technology are used industrially.

[0005] Patent Document 2 discloses an example (comparative example) in which contact is not performed in the absence of olefins, using not only compounds that react with transition metal complexes to form ion pairs, but also organoaluminum oxy compounds. The results show that the example using organoaluminum oxy compounds tends to have a lower molecular weight compared to the example using compounds that react with transition metal complexes to form ion pairs, and there is no disclosure that suggests applying the above pre-contact technique to organoaluminum oxy compounds.

[0006] On the other hand, solid catalysts are preferable for the industrial production of high molecular weight polymers. In particular, many industrial production methods for crystalline ethylene-based polymers and propylene-based polymers utilize processes that use solid catalysts, such as slurry polymerization and gas-phase polymerization. Therefore, it is conceivable that developing a method to obtain high molecular weight polymers using an olefin polymerization catalyst containing a transition metal compound and an organoaluminum oxy compound would be industrially advantageous. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 11-315109 [Patent Document 2] Japanese Patent Publication No. 2002-363210 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] From the above perspective, the object of the present invention is to provide a method for polymerizing olefins that produces high molecular weight olefin polymers with high polymerization activity using a catalyst containing a transition metal compound and an organoaluminum oxy compound. [Means for solving the problem]

[0009] In order to solve the above problems, the inventors conducted research and found that by bringing a transition metal compound into contact with a liquid organoaluminum oxy compound at a specific concentration, followed by polymerization of an olefin, a polymer with a molecular weight nearly 10 times greater than conventional polymers can be obtained, thus completing the present invention.

[0010] The olefin polymerization method according to the present invention is specified by the following requirements [1] to [4]. [1] A method for polymerizing olefins, comprising the steps of: (α) contacting a transition metal compound (A) and a liquid organoaluminum oxy compound (B) under the following conditions (α1) to obtain an olefin polymerization catalyst; and (β) contacting the olefin polymerization catalyst with an olefin. (α1) The concentration of the organoaluminum oxy compound (B) in terms of Al atoms in step (α) is 0.004 to 0.5 mol / l. [2] A method for polymerizing an olefin as described in [1], wherein the transition metal compound (A) is represented by the following general formula (I).

[0011] [ka] [In the formula, M represents a transition metal atom of Group 4 of the periodic table.] m represents an integer from 1 to 6. R 1 ~R 6 These may be identical or different from each other, and represent 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, and two or more of these may be linked to each other to form a ring. Also, when m is 2 or more, R 1 ~R 6 Two of the groups represented by may be linked, n is a number that satisfies 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. When n is 2 or more, the plurality of groups represented by X may be the same as or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. ]]

[0012] [3] In the transition metal compound (A), in the general formula (I), M is Ti, m is 2, and R 1 ~R 6 may be the same as or different from each other, and represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester group, an amide group, an imide group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group or a hydroxy group, and two or more of these may be linked to each other to form a ring. Also, when m is 2 or more, R 1 ~R 6 The olefin polymerization method according to [2], which is a transition metal compound in which two of the groups represented by are linked.

[0013] [4] In the transition metal compound (A), in the general formula (I), R 2 ~R 5 is a hydrogen atom, and R 1 and R 6 are aryl groups, which is the olefin polymerization method according to [2]. [Effect of the Invention]

[0014] As described above, by using the method of the present invention, even existing transition metal compounds can be easily combined with organoaluminum oxy compounds to obtain polymers with high molecular weights, for example, polymers with a weight-average molecular weight close to 10 million. Since this method uses organoaluminum oxy compounds, it can also be used as a supported solid catalyst. Therefore, it is expected to be applicable to slurry polymerization and gas-phase polymerization. [Modes for carrying out the invention]

[0015] The polymerization method for olefins according to the present invention will be described in detail below. In this specification, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" may be used to include not only homopolymers but also copolymers.

[0016] The olefin polymerization method according to the present invention is characterized by comprising the step of obtaining an olefin polymerization catalyst by contacting a transition metal compound (A) and a liquid organoaluminum oxymetal compound (B) under specific conditions. Subsequently, by contacting the olefin polymerization catalyst with an olefin, a polymer with an extremely high molecular weight can be obtained.

[0017] The catalyst components that form the olefin polymerization catalyst used in the olefin polymerization method of the present invention will be described below.

[0018] [Transition metal compound (A)] The transition metal compound (A) according to the present invention can be any known transition metal compound, as long as it is a transition metal compound that can polymerize olefins in combination with an organoaluminum oxy compound. For example, the transition metal compounds disclosed in Patent Documents 1 and 2 are specific examples. A preferred transition metal compound (A) is a compound represented by the following general formula (I).

[0019] [ka] [In the formula, M represents a transition metal atom of Group 4 of the periodic table.] m represents an integer from 1 to 6. R 1 ~R 6 These may be the same or different from each other, and represent 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, and two or more of these may be linked to each other to form a ring, and if m is 2 or more, R 1 ~R 6 Two of the groups shown may be linked together. n is a number that satisfies 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. If n is 2 or more, the multiple groups represented by X may be identical or different from each other, and the multiple groups represented by X may be bonded to each other to form a ring.

[0020] In general formula (I), M is preferably titanium, zirconium, or hafnium, more preferably titanium or zirconium, and particularly preferably titanium. m represents an integer between 1 and 6, preferably between 1 and 4. More preferably, it is 2.

[0021] R 1 ~R 6 Examples of halogen atoms represented by R include fluorine, chlorine, bromine, and iodine. 1 ~R 6Specifically, the hydrocarbon groups represented include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl; linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20, such as vinyl, allyl, and isopropenyl; and linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20, such as ethynyl and propargyl. Examples include: cycloalkyl groups having 3 to 30 carbon atoms, preferably 3 to 20, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl; cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms, such as cyclopentadienyl, indenyl, and fluorenyl; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20, such as phenyl, benzyl, naphthyl, biphenylyl, terphenylyl, phenanthryl, and anthryl; and alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, and di-tert-butylphenyl.

[0022] The above hydrocarbon group may have hydrogen atoms substituted with halogens, for example, halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20, such as trifluoromethyl, pentafluorophenyl, and chlorophenyl. Furthermore, the above hydrocarbon group may be substituted with other hydrocarbon groups, for example, aryl-substituted alkyl groups such as benzyl and cumyl.

[0023] Furthermore, the above hydrocarbon groups include heterocyclic compound residues; oxygen-containing groups such as alkoxy groups, allyloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxyl groups, peroxy groups, and carboxylic acid anhydride groups; nitrogen-containing groups such as amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and amino groups that have been converted to ammonium salts; and borandiyl groups such as boranediyl groups, borantriyl groups, and diboranyl groups. It may also contain sulfur-containing groups such as mercapto groups, thioester groups, dithioester groups, alkylthio groups, arylthio groups, thioacyl groups, thioether groups, thiocyanate groups, isothiocyanate groups, sulfone ester groups, sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups, sulfenyl groups, etc.; phosphorus-containing groups such as phosphine groups, phosphoryl groups, thiophosphoryl groups, phosphat groups, silicon-containing groups, germanium-containing groups, or tin-containing groups.

[0024] Among these hydrocarbon groups, particularly preferred are linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20, such as phenyl, naphthyl, biphenylyl, terphenylyl, phenanthryl, and anthryl; and substituted aryl groups in which these aryl groups are substituted with 1 to 5 substituents, such as halogen atoms, alkyl or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20, or aryl or aryloxy groups having 6 to 30 carbon atoms.

[0025] R 1 ~R 6Examples of oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, and phosphorus-containing groups shown by are the same as those exemplified above. Examples of heterocyclic compound residues shown by R1 to R6 include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine; oxygen-containing compounds such as furan and pyran; sulfur-containing compounds such as thiophene; and groups obtained by further substituting these heterocyclic compound residues with substituents such as alkyl groups and alkoxy groups having 1 to 30, preferably 1 to 20, carbon atoms.

[0026] R 1 ~R 6 Examples of silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, and hydrocarbon-substituted siloxy groups. Specific examples of hydrocarbon-substituted silyl groups include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, and dimethyl(pentafluorophenyl)silyl. Specific examples of hydrocarbon-substituted siloxy groups include trimethylsiloxy. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, and triphenylsilyl are preferred, with trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl being particularly preferred.

[0027] R 1 ~R 6 Examples of germanium-containing groups and tin-containing groups shown include those obtained by substituting the silicon in the silicon-containing group above with germanium or tin. Next, the R explained above 1 ~R 6The following examples will be explained in more detail. Among the oxygen-containing groups, preferred examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc.; preferred examples of allyloxy groups include phenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy, etc.; preferred examples of acyl groups include formyl, acetyl, benzoyl, p-chlorobenzoyl, p-methoxybenzoyl, etc.; and preferred examples of ester groups include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl, etc.

[0028] Among the nitrogen-containing groups, preferred examples include acetamide, N-methylacetamide, and N-methylbenzamide as amide groups; dimethylamino, ethylmethylamino, and diphenylamino as amino groups; acetimide and benzimide as imide groups; and methylimino, ethylimino, propylimino, butylimino, and phenylimino as imino groups.

[0029] Among the sulfur-containing groups, preferred alkylthio groups include methylthio and ethylthio; preferred arylthio groups include phenylthio, methylphenylthio, and nartilthio; preferred thioester groups include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl; preferred sulfone ester groups include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate; and preferred sulfonamide groups include phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide.

[0030] R 1 ~R 6 R 6 It is preferable that R is a substituent other than hydrogen. That is, 6 It is preferable that the group is a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group. In particular, R 6Preferably, the group is a halogen atom; a hydrocarbon group; a heterocyclic compound residue; an oxygen-containing group selected from alkoxy groups, aryloxy groups, acyl groups, ester groups, and hydroxyl groups; a nitrogen-containing group selected from amide groups, amino groups, imide groups, imino groups, cyano groups, and nitro groups; an alkylthio group; a sulfur-containing group selected from arylthio groups, thioester groups, sulfone ester groups, and sulfonamide groups; or a silicon-containing group selected from hydrocarbon-substituted silyl groups and hydrocarbon-substituted siloxy groups. More preferably, the group is a halogen atom, a hydrocarbon group, or a hydrocarbon-substituted silyl group.

[0031] R 6 Preferred hydrocarbon groups include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl; cycloalkyl groups having 3 to 30 carbon atoms, preferably 3 to 20, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20, such as phenyl, benzyl, naphthyl, biphenylyl, and triphenylyl; and groups obtained by further substituting these groups with substituents such as alkyl or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20; halogenated alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20; aryl or aryloxy groups having 6 to 30 carbon atoms, preferably 6 to 20; halogens; cyano groups; nitro groups; hydroxyl groups; and other substituents.

[0032] R 6Preferred hydrocarbon-substituted silyl groups include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, and dimethyl(pentafluorophenyl)silyl. Particularly preferred are trimethylsilyl, triethylphenyl, diphenylmethylsilyl, isophenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, and dimethyl(pentafluorophenyl)silyl.

[0033] R 6 In particular, the group is preferably a branched alkyl group having 3 to 30 carbon atoms, preferably 3 to 20, such as isopropyl, isobutyl, sec-butyl, tert-butyl, and neopentyl; a group in which the hydrogen atoms of these branched alkyl groups are substituted with an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 (such as a cumyl group); a group selected from cycloalkyl groups having 3 to 30 carbon atoms, preferably 3 to 20, such as adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. It is also preferably an aryl group having 6 to 30 carbon atoms, preferably 6 to 20, such as phenyl, naphthyl, fluorenyl, anthryl, and phenanthryl, or a hydrocarbon-substituted silyl group.

[0034] R 1 ~R 6 Two or more of these groups, preferably adjacent groups, may be bonded to each other to form an antimicrobial ring, an aromatic ring, or a hydrocarbon ring containing heteroatoms such as a nitrogen atom, and these rings may further have substituents. When m is 2 or more, R 1 Allies, R 2 Allies, R 3 Allies, R 4 Allies, R 5 Both and R 6 These elements may be identical or different from each other, and any R contained in any one of the ligands may also be included. 1 ~R 6 One of the groups and R contained in the other ligands 1 ~R 6One of the bases may be connected to it.

[0035] n is a number that satisfies the valency of M, specifically an integer between 0 and 5, preferably 1 and 4, and more preferably 1 and 3. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a heterocyclic compound residue, an aluminum-containing group, a halogen-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

[0036] Examples of halogen atoms represented by X include fluorine, chlorine, bromine, and iodine. Examples of hydrocarbon groups represented by X include the above R. 1 ~R 6 Examples similar to those exemplified above include alkyl groups with 1 to 30 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and icosyl; cycloalkyl groups with 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl; alkenyl groups with 2 to 30 carbon atoms such as vinyl, propenyl, and cyclohexenyl; arylalkyl groups with 7 to 30 carbon atoms such as benzyl, phenylethyl, and phenylpropyl; and aryl groups with 6 to 30 carbon atoms such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenylyl, 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 with 1 to 20 carbon atoms is substituted with a halogen. Of these, those with 1 to 20 carbon atoms are preferred.

[0037] The oxygen-containing group represented by X is the above R. 1 ~R 6 Examples similar to those exemplified above include, specifically, hydroxyl groups; alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; and carbonyl groups.

[0038] Specifically, the nitrogen-containing group represented by X is the above-mentioned R 1 ~R 6 Examples similar to those exemplified above include, specifically, amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, and dicyclohexylamino; arylamino groups or alkylarylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino.

[0039] Specifically, the boron-containing group represented by X is BR4 (where R represents hydrogen, an alkyl group, an optionally substituted aryl group, a halogen atom, etc.). The sulfur-containing group represented by X is the above R. 1 ~R 6 Examples similar to those exemplified above include, specifically, sulfonate groups such as methyl sulfonate, trifluoromethanesulfonate, phenyl sulfonate, benzyl sulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, and pentafluorobenzenesulfonate; sulfinate groups such as methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate; alkylthio groups; and arylthio groups.

[0040] Specific examples of phosphorus-containing groups represented by X include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tritlylphosphine; phosphite groups such as methylphosphine, ethylphosphine, and phenylphosphine; phosphonic acid groups; and phosphinic acid groups.

[0041] The heterocyclic compound residue represented by X is the above R 1 ~R 6Examples similar to those exemplified above can be given. Specifically, an aluminum-containing group represented by X is AlR4 (where R represents hydrogen, alkyl group, optionally substituted aryl group, halogen atom, etc.).

[0042] Specifically, halogen-containing groups represented by X include fluorine-containing groups such as PF6 and BF4, chlorine-containing groups such as ClO4 and SbCl6, and iodine-containing groups such as IO4. Specifically, silicon-containing groups represented by X include the above R 1 ~R 6 Examples similar to those exemplified above include, specifically, hydrocarbon-substituted silyl groups such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritrilsilyl, and trinaphthylsilyl; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; and silicon-substituted aryl groups such as trimethylsilylphenyl.

[0043] Specifically, the germanium-containing group represented by X is the above-mentioned R. 1 ~R 6 Examples similar to those exemplified above include, specifically, groups in which the silicon in the silicon-containing group above is replaced with germanium. Specifically, as the tin-containing group represented by X, the above R 1 ~R 6 Examples similar to those exemplified above include groups in which the silicon in the silicon-containing group described above is replaced with tin.

[0044] Furthermore, if n is 2 or greater, the multiple groups represented by X may be identical or different from each other, and the multiple groups represented by X may be bonded together to form a ring.

[0045] X represents a halogen such as Cl or Br, or an alkyl group such as methyl. If there are multiple X's, they may be the same or different from each other. n is determined by the valency of the metal M.

[0046] The following are examples of structural formulas of specific transition metal compounds (A) used in the present invention.

[0047] [ka]

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] (B) Organoaluminum oxy compounds The (B) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminum oxy compound as exemplified in Japanese Patent Application Publication No. 2-78687. Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution by appropriately selecting a solvent.

[0053] (1) A method of reacting the adsorbed water or crystal water with the organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to a suspension containing a compound containing adsorbed water or a salt containing crystal water (for example, magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerium chloride hydrate) and a hydrocarbon solvent.

[0054] (2) A method of directly reacting an organoaluminum compound such as trialkylaluminum with water, ice, or water vapor in a solvent such as benzene, toluene, ethyl ether, or tetrahydrofuran.

[0055] (3) A method of reacting organoaluminum compounds such as trialkylaluminum with organotin oxides such as dimethyltin oxide and dibutyltin oxide in a solvent such as decane, benzene, or toluene.

[0056] The aluminoxane may contain small amounts of organometallic components. The solvent and unreacted organoaluminum compounds may be removed from the aluminoxane solution recovered in each of the above methods by distillation, and the aluminoxane may be further redissolved in the solvent or suspended in a poor solvent.

[0057] Specific examples of organoaluminum compounds used for the production of aluminoxanes are the same as the specific examples of organoaluminum compounds (C-1a) described earlier. Organoaluminum compounds can be used individually or in combination of two or more. Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.

[0058] For the production of aluminoxanes, examples of solvents that can be used include hydrocarbon solvents and ether-based solvents. Specific examples of hydrocarbon solvents 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 fuel; and halides of aromatic hydrocarbons, aliphatic hydrocarbons, or alicyclic hydrocarbons (especially chlorinated or brominated compounds). Specific examples of ether-based solvents include ethyl ether and tetrahydrofuran. Among these, aromatic hydrocarbons and aliphatic hydrocarbons are preferred. When using organoaluminum oxy compounds that are insoluble or sparingly soluble in benzene, the amount of Al component that dissolves in benzene at 60°C is usually 10% or less, preferably 5% or less, and more preferably 2% or less, in terms of Al atoms.

[0059] (B) As an organoaluminum oxy compound, a boron-containing organoaluminum oxy compound represented by the following general formula (4) can also be used.

[0060] [ka]

[0061] (In general formula (4), R 7 This represents a hydrocarbon group with 1 to 10 carbon atoms, or a halogenated hydrocarbon group with 1 to 10 carbon atoms. The four R's 8 Each of these independently represents a hydrogen atom, a halogen atom, and a hydrocarbon group with 1 to 10 carbon atoms. 8 These elements may be identical to each other, but they may also contain one or more different combinations of elements, and these elements may be different from each other.

[0062] A boron-containing organoaluminum oxy compound represented by general formula (4) can be produced, for example, by reacting an alkylboronic acid represented by general formula (5) 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.

[0063] R 7 -B(OH)2···(5) (In general formula (5), R 7 R in the above general formula (4) is 7 (Same group as shown)

[0064] Specific examples of alkylboronic acids represented by general formula (5) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, and 3,5-bis(trifluoromethyl)phenylboronic acid. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These alkylboronic acids can be used individually or in combination of two or more.

[0065] Specific examples of organoaluminum compounds to be reacted with alkylboronic acid are the same as the specific examples of organoaluminum compounds (C-1a) described earlier. Organoaluminum compounds can be used individually or in combination of two or more. Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are more preferred.

[0066] The organoaluminum oxy compounds described above (B) can be used individually or in combination of two or more. In this invention, in addition to the organoaluminum oxy compounds described above, known organometallic compounds and compounds that react with transition metal complexes to form ion pairs can also be used in combination. Specifically, the organometallic compounds described above include organometallic compounds of Groups 1, 2, 12, and 13 of the periodic table as follows.

[0067] (B-1a) General formula RamAl(OR b )nHpXq (In the formula, Ra and Rb may be the same or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; X represents a halogen atom; m is a number where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 0 ≦ q < 3, and m + n + p + q = 3.) An organoaluminum compound represented by the formula.

[0068] (B-1b) General formula M2AlRa4 (In the formula, M2 represents Li, Na, or K; Ra represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.) A complex alkyl compound of a Group 1 metal of the periodic table and aluminum represented by the formula. [[ID=2」]

[0069] (B-1c) General formula RaRbM (In the formula, Ra and Rb may be the same or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; M3 is Mg, Zn, or Cd.) A dialkyl compound of a Group 2 or Group 12 metal of the periodic table represented by the formula.

[0070] Examples of the organoaluminum compounds belonging to the above (B-1a) include the following compounds. General formula RamAl(ORb) 3-m (In the formula, Ra and Rb may be the same or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; m is preferably a number where 1.5 ≦ m ≦ 3.) An organoaluminum compound represented by the formula. General formula RamAlX 3-m (In the formula, Ra represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 < m < 3.) An organoaluminum compound represented by General formula Ram AlH 3-m (In the formula, Ra represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m < 3.) An organoaluminum compound represented by General formula Ram Al(ORb)n Xq (In the formula, Ra and Rb may be the same or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0 < m ≦ 3, n is 0 ≦ n < 3, q is a number of 0 ≦ q < 3, and m + n + q = 3.) An organoaluminum compound represented by

[0071] As the organoaluminum compound belonging to (B-1a), more specifically, trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc. of tri-n-alkylaluminum; 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, etc. of tri-branched chain alkylaluminum; tricyclohexylaluminum, tricyclooctylaluminum, etc. of tricycloalkylaluminum; triphenylaluminum, tritolylaluminum, etc. of triarylaluminum; (i-C4H9)x Aly(C5H 10Trialkenyl aluminum such as triisoprenyl aluminum represented by )z (wherein x, y, and z are positive numbers and z ≥ 2x); alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, and isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; Ra 2.5 Al(ORb) 0.5Partially alkoxylated alkylaluminum having an average composition represented by, etc.; dialkylaluminum allyloxides 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), isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum Examples include alkylaluminum sesquihalides such as nium sesquibromide; partially halogenated alkylaluminum such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, and butylaluminum dibromide; dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, and diisobutylaluminum hydride; other partially hydrogenated alkylaluminum such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; and partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide.

[0072] Compounds similar to (B-1a) can also be used, for example, organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such compounds include (C2H5)2AlN(C2H5)Al(C2H5)2.

[0073] Compounds belonging to the above (B-1b) include LiAl(C2H5)4 and LiAl(C7H 15Examples include 4. In addition, other organometallic compounds such as methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesium, and butylethylmagnesium can also be used.

[0074] Furthermore, compounds that form the above-mentioned organoaluminum compounds within the polymerization system, such as a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium, can also be used. Among organometallic compounds, organoaluminum compounds are preferred. Such organometallic compounds can be used individually or in combination of two or more.

[0075] Examples of compounds that react with transition metal compounds (A) to form ion pairs (hereinafter referred to as "ionized ionic compounds") include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Application Publication No. 3-179005, Japanese Patent Application Publication No. 3-179006, Japanese Patent Application Publication No. 3-207703, Japanese Patent Application Publication No. 3-207704, and U.S. Patent No. 5321106, etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

[0076] Specifically, examples of Lewis acids include compounds represented by BR3 (where R is a phenyl group or fluorine, which may have substituents such as fluorine, a methyl group, or a trifluoromethyl group), such as trifluoroborone, triphenylborone, tris(4-fluorophenyl)borone, tris(3,5-difluorophenyl)borone, tris(4-fluoromethylphenyl)borone, tris(pentafluorophenyl)borone, tris(p-tolyl)borone, tris(o-tolyl)borone, and tris(3,5-dimethylphenyl)borone.

[0077] Examples of ionic compounds include those represented by the following general formula (X).

[0078] [ka]

[0079] In the formula, R 9 Examples include H+, carbonium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptyltrienyl cations, and ferrocenium cations containing transition metals. 10 ~R 13 These may be the same or different from each other, and are organic groups, preferably aryl groups or substituted aryl groups. Specific examples of the above carbonium cations include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0080] Specifically, examples of the above-mentioned ammonium cations 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.

[0081] Specific examples of the phosphonium cations mentioned above include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation. As for Ra, carbonium cations and ammonium cations are preferred, with triphenylcarbonium cation, N,N-dimethylanilinium cation, and N,N-diethylanilinium cation being particularly preferred.

[0082] Other ionic compounds include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Specific examples of trialkyl-substituted ammonium salts include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(m,m-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)boron, and tri(n-butyl)ammonium tetra(o-tolyl)boron.

[0083] Examples of N,N-dialkylanilinium salts include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron. Examples of dialkylammonium salts include di(1-propyl)ammonium tetra(pentafluorophenyl)boron and dicyclohexylammonium tetra(phenyl)boron.

[0084] Furthermore, as ionic compounds, other examples 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 formulas (XI) or (XII).

[0085] [ka]

[0086] (In the formula, Et represents an ethyl group.)

[0087] [ka]

[0088] Examples of borane compounds 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; and salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydridedodecaborate)cobaltate (III) and bis[tri(n-butyl)ammonium]bis(dodecahydridedodecaborate)niclate (III).

[0089] Specific examples of carborane compounds include, for instance, 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-dicarbowndecaborane (13), 2,7-dicarbowndecaborane (13), and undecahydride-7,8-dimethyl -7,8-Dicarboundecaporane, Dodecahydride-11-methyl-2,7-Dicarboundecaporane, Tri(n-butyl)ammonium 1-carbadecaborate, Tri(n-butyl)ammonium 1-carbadodecaborate, Tri(n-butyl)ammonium 1-carbadodecaborate, Tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, Tri(n-butyl)ammonium bromo-1-carbadodecaborate, Tri(n-butyl)ammonium 6-carbadeca Borate (14), tri(n-butyl)ammonium 6-carbadecaborate (12), tri(n-butyl)ammonium 7-carbound decaborate (13), tri(n-butyl)ammonium 7,8-dicalbound decaborate (12), tri(n-butyl)ammonium 2,9-dicalbound decaborate (12), tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicalbound decaborate, tri(n-butyl)ammonium undecahydride-8-ethyl- Salts of anions such as 7,9-dicarboxylate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarboxylate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboxylate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboxylate, and tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carboxylate;Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)ferrate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)cobaltate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)nickelate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)copperate (III), tri(n-butyl)ammonium bis(undekahydride-7,8-dicarbowndecaborate)goldate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbowndecaborate)iron Examples include salts of metal carborane anions such as salts (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboundecaborate)chromate (III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboundecaborate)cobaltate (III), tris[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)chromate (III), bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)cobaltate (III), and bis[tri(n-butyl)ammonium]bis(undekahydride-7-carboundecaborate)nickelate (IV).

[0090] Heteropoly compounds consist of atoms selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titaniummolybdic 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, such as salts 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 with triphenylethyl salts, etc., can be used.

[0091] The ionized compounds described above can be used individually or in combination of two or more. Furthermore, the olefin polymerization catalyst used in the present invention may optionally include a support (D) as described later, insofar as it includes a step in which (A) a transition metal compound and (B) a liquid organic aluminum oxide compound come into contact under specific conditions.

[0092] (D) Carrier The (D) support used as needed in the present invention is an inorganic or organic compound, in the form of a granular or particulate solid. Among these, porous oxides, inorganic chlorides, clays, clay minerals, or ion-exchangeable layered compounds are preferred as inorganic compounds. Specifically, as porous oxides, SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc., or composites or mixtures containing these can be used. For example, natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc., can be used. Among these, those mainly composed of SiO2 and / or Al2O3 are preferred.

[0093] Furthermore, the above inorganic oxide may contain small amounts of carbonates, sulfates, nitrates, and oxide components such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4, Al2(SO4)3, BaSO4, KNO3, Mg(NO3)2, Al(NO3)3, Na2O, K2O, and Li2O. While the properties of such porous oxides vary depending on the type and manufacturing method, the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of ​​50 to 1000 m². 2 / g, preferably 100-700m 2 It is in the range of / g, and the pore volume is 0.3-3.0 cm³. 3 It is desirable that the weight be within the range of / g. Such carriers are used after being calcined at 100-1000°C, preferably 150-700°C, as needed.

[0094] Inorganic chlorides such as MgCl2, MgBr2, MnCl2, and MnBr2 can be used. These inorganic chlorides may be used as is, or they may be used after being crushed using a ball mill or vibration mill. Alternatively, the inorganic chlorides may be dissolved in a solvent such as alcohol, and then precipitated into fine particles using a precipitating agent. The clay used in this invention is typically composed mainly of clay minerals. The ion-exchangeable layered compounds used in this invention are compounds having a crystalline structure in which planes formed by ionic bonds are stacked parallel to each other with weak bonding forces, and the ions they contain are exchangeable. Most clay minerals are ion-exchangeable layered compounds. Furthermore, these clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products; artificially synthesized materials can also be used.

[0095] Furthermore, examples of clay, clay minerals, or ion-exchangeable layered compounds include clay, clay minerals, and ionic crystalline compounds having layered crystalline structures such as hexagonal close-packing type, antimony type, CdCl2 type, and CdI2 type. Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gylome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, lyokdiite group, palygorskite, kaolinite, nacrite, dickite, and halloysite. Examples of ion-exchangeable layered compounds include crystalline acidic salts of polyvalent metals such as α-Zr(HAsO4)2·H2O, α-Zr(HPO4)2, α-Zr(KPO4)2·3H2O, α-Ti(HPO4)2, α-Ti(HAsO4)2·H2O, α-Sn(HPO4)2·H2O, γ-Zr(HPO4)2, γ-Ti(HPO4)2, and γ-Ti(NH4PO4)2·H2O.

[0096] Such clays, clay minerals, or ion-exchangeable layered compounds are preferably those with a pore volume of 0.1 cc / g or more, measured by mercury intrusion with a radius of 20 Å or more, and particularly preferably those with a pore volume of 0.3 to 5 cc / g. Here, the pore volume is measured by mercury intrusion using a mercury porosimeter, with a pore radius of 20 to 3 × 10 4 Measurements are taken in the range of Å.

[0097] When a support material with 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 chemically treat clay and clay minerals. Chemical treatments can be used, including surface treatments to remove impurities attached to the surface and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment. Acid treatment removes surface impurities and increases the surface area by eluting cations such as Al, Fe, and Mg in the crystalline structure. Alkali treatment destroys the crystalline structure of the clay, leading to a change in its structure. Salt treatment and organic treatment can form ionic complexes, molecular complexes, organic derivatives, etc., which can change the surface area and interlayer distance.

[0098] Ion-exchangeable layered compounds may be layered compounds in which the interlayers are expanded by utilizing ion exchange properties and exchanging the exchangeable ions between layers with other large, bulky ions. Such bulky ions play a supporting role in the layered structure and are usually called pillars. The introduction of another substance between the layers of a layered compound in this way is called intercalation. Guest compounds for intercalation include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (where R is a hydrocarbon group, etc.), and [Al13O4(OH) 24 ]7+,[Zr4(OH) 14 Examples include metal hydroxide ions such as ]2+ and [Fe3O(OCOCH3)6]+. These compounds can be used individually or in combination of two or more. When intercalating these compounds, polymers obtained by hydrolyzing metal alkoxides (where R is a hydrocarbon group, etc.) such as Si(OR)4, Al(OR)3, and Ge(OR)4, or colloidal inorganic compounds such as SiO2 can also be present. Examples of pillars include oxides produced by heating and dehydrating after intercalating the above-mentioned metal hydroxide ions between layers.

[0099] Clay, clay minerals, and ion-exchangeable layered compounds may be used as is, or after being subjected to treatments such as ball milling or sieving. They may also be used after being newly treated with water adsorption or heat dehydration. Furthermore, they may be used individually or in combination of two or more. Of these, clay or clay minerals are preferred, and montmorillonite, vermiculite, pectolite, teniolite, and synthetic mica are particularly preferred.

[0100] Examples of organic compounds include granular or particulate solids with particle sizes ranging from 10 to 300 μm. Specifically, 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.

[0101] (E) Organic compound component In the present invention, (E) organic compound component is used as needed to improve polymerization performance and the physical properties of the resulting polymer. Examples of such organic compounds include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

[0102] Alcohols and phenolic compounds are typically represented as Rf-OH, where Rf represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms. For alcohols, those in which Rf is a halogenated hydrocarbon are preferred. For phenolic compounds, those in which the α,α'-positions of the hydroxyl group are substituted with hydrocarbons having 1 to 20 carbon atoms are preferred.

[0103] As carboxylic acids, those represented by Rg-COOH are usually used. Rg represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, with halogenated hydrocarbon groups having 1 to 50 carbon atoms being particularly preferred. As phosphorus compounds, phosphoric acids having a POH bond, P-OR, phosphates having a P=O bond, and phosphine oxide compounds are preferred. As sulfonates, those represented by the following general formula (XIII) are examples.

[0104] [ka]

[0105] [In the formula, M is an element from groups 1 to 14 of the periodic table. Rh is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. m is an integer from 1 to 7, and n is 1 ≤ n ≤ 7.]

[0106] (Method of polymerization of olefins) In the present invention, a catalyst for olefin polymerization is obtained by contacting the above-mentioned (A) transition metal compound with (B) a liquid organoaluminum oxy compound. Subsequently, the olefin polymerization catalyst is brought into contact with an olefin. (Step (α)) The above contact step is preferably carried out in a state in which the olefin is substantially absent. Specifically, it is preferable that the conditions are such that the amount of olefin is less than 1 gram per millimoles of metal atoms of the (A) transition metal compound. More preferably it is 0.5 grams or less, and even more preferably 0.1 grams or less.

[0107] Here, a state where olefins are substantially absent means a state in which olefins are present in an amount equal to or greater than that of the transition metal compound (A). Contact between the transition metal compound (A) and the liquid organoaluminum oxy compound (B) is carried out in solution. Specifically, for example, a solution or suspension in which component (A) is dissolved or suspended in a saturated hydrocarbon or aromatic hydrocarbon is brought into contact with component (B). If component (A) is in a suspension state, stirring or other methods are performed until a homogeneous solution is obtained.

[0108] In the present invention, when bringing component (A) and component (B) into contact, it is crucial to keep the concentration of component (B) within a certain range. Specifically, the concentration of (α1) liquid organoaluminum oxy compound, in terms of Al atoms, is in the range of 0.004 to 0.5 mol / l. A preferred lower limit is 0.007 mol / l, more preferably 0.01 mol / l, and even more preferably 0.02 mol / l. On the other hand, a preferred upper limit is 0.4 mol / l, more preferably 0.2 mol / l.

[0109] When contact is made within this concentration range, it tends to be possible to obtain polymers with higher molecular weights than conventional methods when used in the polymerization of olefins. The reason for this effect is currently unknown, but the inventors have speculated as follows.

[0110] When component (A) and component (B) come into contact under the conditions described above, the interaction between component (A) and component (B) progresses, and the active species of olefin polymerization, mainly composed of component (A), becomes less susceptible to chain transfer. For example, hydrogen by-production during polymerization is less likely to occur, and many olefins can easily coordinate, creating an environment where growth reactions are preferred over olefin-mediated chain transfer reactions. As a result, the molecular weight of the resulting polymer increases.

[0111] In environments with low concentrations below the lower limit of the above concentration, for example, in environments with low Al atom concentrations such as those used in olefin polymerization reactions, the unique structure described above may not be formed. However, if the concentration exceeds the upper limit, the interactions may become excessive, making it impossible to maintain the structure of the active species as described above.

[0112] The order of contact is as follows: component (B) may be added to the solution or suspension containing component (A), or component (B) may be added to the solution or suspension containing component (A). The contact between component (A) and component (B) is preferably between -15°C and 100°C. A more preferable lower limit is -10°C, even more preferably 10°C, particularly preferably 20°C, and especially preferably 30°C. On the other hand, a more preferable upper limit is 80°C, and even more preferably 70°C. If the temperature is too low, the above-mentioned interaction will not occur easily, and the reaction will be insufficient. Conversely, if the temperature is too high, the transition metal compound itself may change. This is especially likely to occur when the transition metal compound takes on a complex structure. The contact time in the above process is preferably 1 minute to 20 hours. A more preferable lower limit is 5 minutes, even more preferably 8 minutes, and particularly preferably 10 minutes. On the other hand, a more preferable upper limit is 10 hours, even more preferably 5 hours, and particularly preferably 2 hours. If the time is too short, the above-mentioned effects may not occur sufficiently. On the other hand, if the time is too long, there is a risk of excessive effects as described above, and it may lead to a decrease in productivity.

[0113] The ratio of components (A) and (B) when they are brought into contact is the molar ratio [(B) / M] of the transition metal atoms (M) in component (A) to the aluminum atom equivalent value of component (B), which is usually in the range of 0.1 to 100,000, preferably 1.0 to 10,000, and particularly preferably 2.0 to 5,000. In the present invention, at least component (A) and component (B) of the catalyst components that form the olefin polymerization catalyst as described above are brought into contact in a state where olefin is substantially absent, but component (C) may also be brought into contact at this time. Alternatively, one of component (A) and component (B) may be supported on component (D) and then brought into contact with the other component.

[0114] When component (A) and component (B) are brought into contact with other components, it is preferable to contact the contact product of component (A) and component (B) with other components after contacting component (A) and component (B). Other components, such as the above-mentioned organometallic compound and ionized compound, component (D), and component (E), are preferably contacted with the contact product of component (A) and component (B) in a state dissolved or suspended in a saturated hydrocarbon, aromatic hydrocarbon or halogenated hydrocarbon.

[0115] The contact temperature between the contact product of component (A) and component (B) and component (C) is -78°C to 100°C, preferably 0°C to 80°C, and the contact time is usually 10 seconds to 5 hours, preferably 1 minute to 2.5 hours, particularly preferably 1 minute to 1 hour. The amount ratio of other components to the contact product when the contact product of component (A) and component (B) is contacted with other components is the molar ratio ((C) / M) of component (C) to the transition metal atom (M) of component (A) in the contact product, and is usually in the range of 1 to 10, preferably 1 to 5.

[0116] The contact product of component (A) and component (B) contacted as described above, or the contact product of component (A), component (B) and other components, may be directly fed into a reactor in which olefin is present, or the contact product may be fed into the reactor together with olefin. Further, the contact product of component (A) and component (B), or the contact product of component (A), component (B) and other components, may be supported on component (D).

[0117] s In addition to component (B) contacted with component (A) as described above, for the purpose of inactivating moisture and impurities in the polymerization system, etc., component (B) and the above-mentioned organometallic compound can be separately added to the reactor. During polymerization, the method of supplying the contact product of component (A) and component (B) to the reactor is arbitrary, and known methods can be used without limitation.

[0118] When polymerizing olefin in the presence of the above olefin polymerization catalyst, component (A) is usually 10 -12 ~10 -2 moles, preferably 10 -10~10 -3 It is used in amounts that correspond to moles. In this invention, even when component (A) is used at a relatively low concentration, olefins can be polymerized with high polymerization activity.

[0119] Component (B) is used in such an amount that its molar ratio ((B) / M) with the transition metal atoms (M) in component (A) is typically 0.1 to 100,000, preferably 0.5 to 50,000, and particularly preferably 1.0 to 10,000. Component (C) is used in such an amount that its molar ratio ((C) / M) with the transition metal atoms (M) in component (A) is typically 1 to 10, preferably 1 to 5.

[0120] Component (E) is used in an amount such that the molar ratio ((E) / (B)) of component (B) is usually 0.01 to 10, preferably 0.1 to 5. In the present invention, polymerization can be carried out by either liquid-phase polymerization methods such as dissolution polymerization or suspension polymerization, or by gas-phase polymerization methods. Specific examples of inert hydrocarbon media used in liquid-phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof. Olefins themselves can also be used as polymerization solvents.

[0121] Furthermore, the polymerization temperature of olefins using such olefin polymerization catalysts is typically in the range of -50 to +200°C, preferably 0 to 170°C. The polymerization pressure is typically under atmospheric pressure to 9.8 MPa (atmospheric pressure to 100 kg / cm²), preferably atmospheric pressure to 4.9 MPa (atmospheric pressure to 50 kg / cm²), and the polymerization reaction can be carried out by batch, semi-continuous, or continuous methods. It is also possible to carry out polymerization in two or more stages with different reaction conditions.

[0122] The molecular weight of the resulting olefin polymer can be adjusted by introducing hydrogen into the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of component (A) used. Olefins that can be polymerized by the method of the present invention include linear or branched α-olefins having 2 to 30 carbon atoms, preferably 2 to 20, such as ethylene, propylene, 1-butene, 2-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, 1-eicosene; and cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetra Cyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene; polar monomers, such as α,β-unsaturated carboxylic acids including acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid anhydride, and metal salts thereof such as sodium salts, potassium salts, lithium salts, zinc salts, magnesium salts, and calcium salts; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid Examples include α,β-unsaturated carboxylic acid esters such as tert-butyl, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate; vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; unsaturated glycidyls such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconic acid ester; and vinyl chloride. Vinylcyclohexane, dienes, and polyenes can also be used.

[0123] As the diene or polyene, cyclic or chain-like compounds having 4 to 30 carbon atoms, preferably 4 to 20, and possessing two or more double bonds are used. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4-ethylidene-8- Examples include methyl-1,7-nonadien, 5,9-dimethyl-1,4,8-decatriene, and 4,8-dimethyl-1,4,8-decatriene; as well as aromatic vinyl compounds, such as mono- or polyalkylstyrenes including 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, p-chlorostyrene, and divinylbenzene; and 3-phenylpropylene, 4-phenylpropylene, and α-methylstyrene. These olefins can be used individually or in combination of two or more.

[0124] The olefin polymerization method according to the present invention exhibits high polymerization activity and can produce polymers with a narrow molecular weight distribution. Furthermore, when two or more olefins are copolymerized, an olefin copolymer with a narrow compositional distribution can be obtained. The molecular weight of the polymer obtained by the olefin polymerization method of the present invention can be adjusted by using a chain transfer agent such as hydrogen or by controlling the polymerization temperature. If a chain transfer agent such as hydrogen is not used, for example, polymers with a weight-average molecular weight of 3 million or more, preferably 4 million or more, more preferably 5 million or more, and particularly preferably 6 million or more can be produced even at an industrially advantageous polymerization temperature of 50°C or higher. The molecular weight of the polymer obtained by this method without using a chain transfer agent such as hydrogen can also be considered as one indicator for evaluating the high molecular weight potential of the catalyst.

[0125] The molecular weight of a polymer can also be evaluated by its intrinsic viscosity [η], a method that has been known for some time. The intrinsic viscosity [η] of the polymer obtained by the polymerization method of the present invention is preferably 20 dl / g or more, more preferably 25 dl / g or more, even more preferably 30 dl / g or more, particularly preferably 35 dl / g or more, and especially preferably 40 dl / g or more, when no chain transfer agent such as hydrogen is used. Furthermore, it is known empirically that the weight-average molecular weight and intrinsic viscosity [η] satisfy the following relationship in the case of ethylene polymers, for example. [η] = 6.2 * 10 -4 *Mw 0.7

[0126] Using the above formula, the intrinsic viscosity [η] can be calculated and predicted from the weight-average molecular weight measured by the GPC. Such polymers can be applied to known uses such as high-strength fibers, high-strength sheets, lithium-ion batteries, and separator films for capacitors. Applications that take advantage of the strength inherent in their high molecular weight are particularly desirable. [Examples]

[0127] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0128] [Weight-average molecular weight (Mw), molecular weight distribution (Mw / Mn) of polymers] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the olefin polymer were determined by gel permeation chromatography (GPC). The calculations were performed using molecular weight distribution curves obtained from a Waters Alliance GPC 2000 gel permeation chromatograph (high-temperature size exclusion chromatograph), under the following operating conditions: <Equipment and conditions used> Measurement device: Gel permeation chromatograph allianceGPC2000 model (Waters Corporation) Analysis software; Chromatography data system Empower (trademark, Waters Inc.) Column; TSKgel GMH6-HT×2 + TSKgel GMH6-HT×2 (Inner diameter 7.5mm x length 30cm, Tosoh Corporation) Mobile phase: o-dichlorobenzene [=ODCB] (Wako Pure Chemical Industries, 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: 1 second Sample concentration: 0.15% (w / v) Molecular weight calibration for monodisperse polystyrene (Tosoh Corporation) / molecular weight from 495 to 20.6 million

[0129] (Example 1) A dry, 1.5-liter pressure-resistant autoclave was thoroughly purged with nitrogen, and 450 ml of dehydrated cyclohexane and 50 ml of hexane were charged under a nitrogen stream. The temperature was then raised to 50°C, and ethylene was supplied to maintain an internal pressure of 0.5 MPa gauge pressure.

[0130] Meanwhile, a 0.4 mmol / liter toluene solution of the following compound was prepared in a 25 ml glass container purged with nitrogen. A 1.0 mol / liter solution of methylaluminoxane from Tosoh Finechem Co., Ltd. (calculated in terms of aluminum atoms) was added to achieve an Al / Ti molar ratio of 300, and the mixture was stirred at 50°C for 20 minutes. (Toluene and other substances were added to adjust the concentration to 0.1 mol / liter of Al during this contact step.)

[0131] Subsequently, 0.002 millimoles of the above contact solution (in terms of Ti atoms) was added to the polymerizer, and polymerization was started. (Aluminum concentration during polymerization: 0.0012 mol / liter) Ethylene was supplied while maintaining an internal temperature of 50°C, and the internal pressure was maintained at 0.5 MPa gauge pressure. The polymerization time was 5 minutes.

[0132] [ka] After a predetermined time had elapsed, the supply of ethylene was stopped and a small amount of methanol was added. Next, the resulting polymer solution was added to 3 liters of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with methanol, it was dried under reduced pressure at 80°C for 10 hours. The resulting polyethylene was 683 milligrams, and the polymerization activity was 4.1 kg / mmol-Ti·hr. The weight-average molecular weight (Mw) of the resulting polymer, as measured by GPC, was 8.24 million, and the molecular weight distribution (Mw / Mn: Mn is the number-average molecular weight) was 2.96.

[0133] (Comparative Example 1) Without performing the aforementioned contact step, ethylene polymerization was carried out in the same manner as in Example 1, except that a 1 mol / liter solution of methylaluminoxane from Tosoh Finechem Co., Ltd. (calculated in terms of aluminum atoms) was added to an autoclave to achieve an Al / Ti ratio of 300, and 0.0002 millimoles (calculated in terms of Ti atoms) was added to the polymerizer. (Aluminum concentration during polymerization: 0.00012 mol / liter) The polymer yield was 662 milligrams, the polymerization activity was 39.7 kg / mmol-Ti·hr, the weight-average molecular weight was 930,000, and the molecular weight distribution (Mw / Mn) was 3.2. The results above show that the olefin polymerization method of the present invention exhibits a unique effect compared to conventional methods, where the molecular weight increases by more than 10 times while maintaining almost the same molecular weight distribution. Therefore, it is possible to obtain ethylene polymers with very high molecular weights while having a relatively homogeneous molecular weight distribution. This demonstrates that, through relatively simple processing, the catalyst of the present invention can remarkably be transformed into a unique property in which chain transfer is unlikely to occur, while the active species remain relatively homogeneous.

Claims

1. The process includes a step (α) of contacting a transition metal compound (A) and a liquid organoaluminum oxy compound (B) at 30 to 100°C under the following conditions (α1) to obtain an olefin polymerization catalyst, and a step (β) of contacting the olefin polymerization catalyst with an olefin. A method for polymerizing an olefin represented by the following general formula (I), wherein the transition metal compound (A) is (A). (α1) The concentration of the organoaluminum oxy compound (B) in terms of Al atoms after contact in step (α) is 0.004 to 0.5 mol / l. 【Chemistry 1】 [In the formula, M represents a transition metal atom of Group 4 of the periodic table.] m represents an integer from 1 to 6. R 1 ~R 6 These may be identical or different from each other, and represent 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, and two or more of these may be linked to each other to form a ring. Also, if m is 2 or more, R 1 ~R 6 Two of the groups shown may be linked together. n is a number that satisfies 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. If n is 2 or more, the multiple groups represented by X may be the same or different from each other, and the multiple groups represented by X may be bonded to each other to form a ring.

2. The transition metal compound (A) is such that in the general formula (I), M is Ti, m is 2, and R 1 ~R 6 The polymerization method for olefins according to claim 1, characterized in that the following groups may be the same or different from each other, and represent a transition metal compound that includes a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an allyloxy group, an arylthio group, an acyl group, an ester group, a thioester group, an amide group, an imide group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group, or a hydroxyl group, and two or more of these may be linked to each other to form a ring.

3. The transition metal compound (A) is, in the general formula (I), R 2 ~R 5 is a hydrogen atom, and R 1 and R 6 is an aryl group. The method for polymerizing an olefin according to claim 1

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