Metallocene compounds, catalysts for olefin polymerization, methods for producing catalysts for olefin polymerization, and methods for producing olefin polymers.

Abstract

To provide a metallocene compound that has excellent solvent solubility and also has a sufficient capability as a catalyst component, a catalyst for olefinic polymerization containing the same, a method for producing the catalyst, and a method for producing an olefinic polymer.SOLUTION: The present invention provides a metallocene compound represented by a specific formula, having a chemical structure with a specific substituent introduced to a xylene skeleton constituting a crosslinked part of the metallocene compound comprising an orthoxylenebisindenyl complex. A catalyst for olefinic polymerization is produced by bringing the metallocene compound (component (A)) into contact with a compound (component (B)) that reacts with the component (A) to form a cationic metallocene compound, with a particulate carrier (component (C)), and further optionally with an organic aluminum compound (component (D)).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a metallocene compound, a catalyst for olefin polymerization containing the same, a method for producing the olefin polymerization catalyst, and a method for producing an olefin polymer using the olefin polymerization catalyst. More specifically, the invention relates to a metallocene compound having a basic skeleton structure in which two indenyl rings are crosslinked with an ortho-phenylenedimethylene structure, a catalyst for olefin polymerization containing the same, a method for producing the olefin polymerization catalyst, and a method for producing an olefin polymer using the olefin polymerization catalyst. [Background technology]

[0002] The cross-linking structure of metallocene compounds aims to fix the arrangement and shape of the entire complex molecule, and common examples of such cross-linking structures include methylene, isopropylidene, ethylene, and dimethylsilylene. By cross-linking two ligands within a metallocene compound, it becomes possible to control the molecular weight of the resulting polymer and its reactivity with α-olefins when the metallocene compound is subjected to polymerization reactions of olefins. Furthermore, in the polymerization reaction of propylene, cross-linking structures are considered a particularly effective means of controlling stereoregularity. Non-patent document 1 describes a method for synthesizing a zirconium complex in which two indenyl rings are bridged with an ortho-phenylenedimethylene structure, and the two isomers obtained (racemic and meso). 1 The results of 1H-NMR measurements and mass spectral analysis are described. Furthermore, the results of ethylene polymerization and propylene polymerization using methylaluminoxane as a co-catalyst are reported. Patent Document 1 describes a catalyst combining a zirconium complex, in which two indenyl rings are crosslinked with an ortho-phenylenedimethylene structure, and methylaluminoxane as a method for obtaining olefin polymers with sufficiently high molecular weight suitable for industrial applications. It describes that using this catalyst, highly active high molecular weight polymers can be produced by solution polymerization of ethylene homopolymerization at 70°C and ethylene / 1-hexene copolymerization at 40°C. It also describes that highly active high molecular weight polymers can be produced by ethylene / 1-butene copolymerization at ultra-high pressure (800 bar) at 180°C. Patent Document 2 describes the results of ethylene / propylene copolymerization and ethylene / propylene / diene copolymerization using a catalyst that combines a zirconium complex in which unsubstituted indenyl rings or substituted indenyl rings are crosslinked with an ortho-phenylenedimethylene structure with a methylalmoxane. Non-patent document 2 describes a method for synthesizing a zirconium complex in which two indenyl rings having methyl groups at positions 5 and 6 are bridged with an ortho-phenylenedimethylene structure, and the temperature-controlled properties of the resulting racemic mixture. 1 The results of 1H-NMR measurements are described. Non-patent document 2 also describes the results of ethylene / 1-hexene copolymerization, reporting that due to changes in the complex conformation during polymerization, the resulting copolymer has a broad molecular weight distribution, and that two types of copolymers with different 1-hexene content can be obtained.

[0003] None of the above non-patent and patent documents mention the solubility in organic solvents of metallocene compounds in which two indenyl rings are crosslinked with an ortho-phenylenedimethylene structure. Generally, metallocene compounds of unsubstituted cyclopentadiene, indene, and fluorene have low solubility in organic solvents such as toluene, and a large amount of organic solvent is required to completely dissolve the metallocene compound. Therefore, metallocene compounds with low solubility have the problem of low extraction efficiency with organic solvents in the purification process during manufacturing. In addition, when manufacturing supported catalysts of metallocene compounds, it is preferable to completely dissolve the metallocene compound in the organic solvent in order to uniformly support it on the support. For these reasons, metallocene compounds with a structure that has appropriate solubility in organic solvents are desired. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 9-286812 [Patent Document 2] Japanese Patent Publication No. 10-67817 [Non-patent literature]

[0005] [Non-Patent Document 1] Macromolecules, 1995, vol.28, p.4801-4805 [Non-Patent Document 2] Macromolecular Chemistry and Physics, 2002, vol.203, p.1301-1308 [Overview of the project] [Problems that the invention aims to solve]

[0006] It is generally known that substituent manipulation, such as introducing substituents to the basic skeleton of a compound, replacing the original substituent with a different one, or removing the original substituent, can be effective in adjusting the solvent solubility of a compound. However, when adjusting the solvent solubility of a metallocene compound used as a catalyst, substituent manipulation can improve solvent solubility, but it may also reduce the catalytic ability of the metallocene compound. In view of the above circumstances, the present invention aims to provide a metallocene compound that exhibits excellent solvent solubility and also possesses sufficient catalytic activity by introducing substituents to a metallocene compound consisting of a crosslinked bisindenyl complex. Furthermore, the present invention also aims to provide a catalyst for olefin polymerization having high polymerization activity with such metallocene compounds, and a method for producing the same. Another objective of the present invention is to provide a method for producing olefin polymers, particularly ethylene-based polymers, using such olefin polymerization catalysts. [Means for solving the problem]

[0007] The metallocene compound of the present invention is a metallocene compound represented by the following general formula (1).

[0008] [ka]

[0009] [In general formula (1), M represents one of the transition metals Ti, Zr, or Hf. X 1 and X 2 Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, a hydrocarbon group substituted with 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. R 1 , R 2 , R 3 , R4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, and R 1 ~R 16 Among the adjacent atoms or groups may be bonded to each other to form a cyclic structure together with the atoms to which they are bonded. However, at least one of R 1 , R 2 , R 3 and R 4 represents an atom or group other than a hydrogen atom.]

[0010] In the general formula (1), R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and at least one of them may be an atom or group other than a hydrogen atom.

[0011] In one embodiment, the olefin polymerization catalyst of the present invention is characterized by containing the following components (A) and (B). Component (A): A metallocene compound represented by the above general formula (1) Component (B): A compound that reacts with component (A) to form a cationic metallocene compound

[0012] Furthermore, in another embodiment, the olefin polymerization catalyst of the present invention is characterized by comprising the following components (A), (B), and (C). Component (A): Metallocene compound represented by the above general formula (1) Component (B): A compound that reacts with component (A) to produce a cationic metallocene compound. Ingredient (C): Particulate carrier

[0013] In any of the above embodiments of the catalyst for olefin polymerization, component (B) may be an aluminoxane, and component (C) may be silica. Furthermore, any embodiment of the olefin polymerization catalyst described above may also contain component (D) an organoaluminum compound.

[0014] In another embodiment, the olefin polymerization catalyst of the present invention is an olefin polymerization catalyst comprising at least the following components (A) and (B) in contact. Component (A): Metallocene compound represented by the above general formula (1) Component (B): A compound that reacts with component (A) to produce a cationic metallocene compound.

[0015] In another embodiment, the olefin polymerization catalyst of the present invention is an olefin polymerization catalyst obtained by contacting at least the following components (A), (B), and (C). Component (A): Metallocene compound represented by the above general formula (1) Component (B): A compound that reacts with component (A) to produce a cationic metallocene compound. Ingredient (C): Particulate carrier

[0016] In any of the above embodiments of the olefin polymerization catalyst, the catalyst can be further obtained by contacting it with component (D) an organoaluminum compound.

[0017] In one embodiment, the method for producing an olefin polymerization catalyst of the present invention is characterized by contacting components (A) and (B).

[0018] Furthermore, in another embodiment, the method for producing the olefin polymerization catalyst of the present invention is characterized by contacting the components (A), (B), and (C).

[0019] The above method may also include the following steps. Step 1: Mix component (A) with a hydrocarbon solvent to prepare complex solution a.

[0020] The above method may also include the following steps 2 and 3. Step 2: Mix the complex solution a obtained in Step 1 with component (B) to prepare a mixed solution b. Step 3: Mix the mixture b and component (C) to prepare slurry c.

[0021] The above method may also include the following step 4. Step 4: Dry the slurry c obtained in Step 3.

[0022] In any embodiment of the above method, in step 1, the molar concentration of component (A) in the complex solution a can be 2.5 mmol / L or more and 100 mmol / L or less. Furthermore, in any embodiment of the above method, in step 1, the molar concentration of component (A) in the complex solution a can be 3.0 mmol / L or more and 50 mmol / L or less.

[0023] In any embodiment of the above method, the amount of component (B) used can be greater than 0.1 and less than or equal to 100,000 in terms of its molar ratio with component (A) [component (B) / component (A)].

[0024] In one embodiment, the method for producing an olefin polymer of the present invention is characterized by polymerizing or copolymerizing an olefin monomer in the presence of the above-mentioned olefin polymerization catalyst. Furthermore, in another embodiment, the method for producing an olefin polymer of the present invention is characterized by polymerizing or copolymerizing an olefin monomer in the presence of an olefin polymerization catalyst produced by the above method.

[0025] In one embodiment, the above-described method for producing the olefin polymer can polymerize or copolymerize an olefin monomer containing at least ethylene. [Effects of the Invention]

[0026] According to the present invention, by introducing specific substituents onto the xylene skeleton constituting the crosslinked portion of a metallocene compound consisting of an orthoxylenebisindenyl complex, a metallocene compound is provided that exhibits excellent solvent solubility and also possesses sufficient catalytic activity. Furthermore, by using such metallocene compounds, it is possible to prepare a complex solution containing a high concentration of metallocene compounds that also possess sufficient catalytic activity, thereby enabling the production of catalysts with high polymerization activity. The catalyst provided by the present invention can be used to polymerize or copolymerize olefin monomers, and in particular can efficiently produce ethylene polymers. [Modes for carrying out the invention]

[0027] The metallocene compound provided in the present invention is represented by the general formula (1) described later and is characterized by having a chemical structure in which a specific substituent is introduced on the xylene skeleton that constitutes the crosslinking portion of the metallocene compound consisting of an orthoxylenebisindenyl complex. By introducing a specific substituent on the xylene skeleton that constitutes the crosslinking portion of the metallocene compound consisting of an orthoxylenebisindenyl complex, a metallocene compound is obtained that has excellent solvent solubility and also possesses sufficient ability as a catalytic component. The reasons for obtaining such metallocene compounds are not bound by any particular theory, but the main reasons are thought to be as follows. When the crosslinked portion of a metallocene compound, where two ligands are crosslinked, is an orthoxylene structure, the angle between two opposing ligands, such as two indenyl ligands, is narrower than in the case of a silylene crosslink with one silicon atom (e.g., -Si(R)2- (where R represents a substituent)) or a methylene crosslink with one carbon atom (e.g., -C(R)2- (where R represents a substituent)). Therefore, substituents on the indenyl ligands present within the orthoxylenebisindenyl complex have a high shielding effect on the polymerization field and may suppress the coordination insertion of monomers. On the other hand, the crosslinked portion is sterically far from the polymerization field, and substituents on the crosslinked portion do not shield the polymerization field. Furthermore, it is presumed that the electronic influence on the polymerization field via bonding is small, and therefore it has little effect on polymerization activity. Consequently, while introducing substituents on indenyl ligands can improve solvent solubility but may decrease polymerization activity, introducing substituents on the crosslinked portion can improve solvent solubility without decreasing polymerization activity.

[0028] The metallocene compounds of the present invention exhibit excellent solvent solubility and possess sufficient catalytic activity, thus providing the following advantageous effects from the synthesis stage to their use as polymerization catalysts. (1) Because metallocene compounds are readily soluble in solvents during synthesis and purification, metallocene compounds can be produced efficiently. (2) Because it is easily soluble in solvents during catalyst preparation and possesses the ability to elicit high polymerization activity, a polymerization catalyst with high polymerization activity can be obtained by preparing a high-concentration complex solution, and the destabilization or failure of catalyst performance due to undissolved residue can be avoided.

[0029] This invention does not exclude the introduction of substituents on the indenyl ligand of metallocene compounds consisting of orthoxylenbisindenyl complexes. If the metallocene compound of the present invention has substituents not only on the xylene skeleton, which is the crosslinking portion, but also on the indenyl ligand, depending on the position or type of substituent on the indenyl ligand, a shielding effect on the polymerization field may occur, potentially reducing polymerization activity. On the other hand, the substituents on the xylene skeleton and the indenyl ligand improve solvent solubility, potentially leading to higher polymerization activity. Therefore, even if polymerization activity decreases due to the shielding effect on the polymerization field, this decrease in polymerization activity is considered to be offset by the improvement in polymerization activity due to the improved solvent solubility. Therefore, when using a metallocene compound consisting of an orthoxylenebisindenyl complex having substituents on both the xylene skeleton (which forms the crosslinking portion) and the indenyl ligand, a catalyst with higher polymerization activity can be prepared compared to when using a metallocene compound consisting of an orthoxylenebisindenyl complex having substituents only on the indenyl ligand. Furthermore, if the shielding effect of the substituent on the indenyl ligand is not very strong, the improved solvent solubility effect of the substituent on the xylene skeleton (which forms the crosslinking portion) can result in polymerization activity that surpasses that of an orthoxylenebisindenyl complex with no substituents on the indenyl ligand.

[0030] The present invention will be described below. In this invention, "polymerization" refers collectively to the homopolymerization of one type of monomer and the copolymerization of multiple types of monomers. When there is no need to distinguish between the two, the term "polymerization" is used collectively. Furthermore, in this invention, the "~" indicating a numerical range is used to mean that the numerical values ​​written before and after it are included as the lower and upper limits, respectively. Furthermore, in this specification, general formula (1) is used with the intention of encompassing both meso and racemic compounds without distinction. When it is necessary to distinguish between meso and racemic compounds included in general formula (1), it shall be clearly indicated that they are either meso or racemic compounds. In this invention, "Ph" represents phenyl or a phenyl group, "Me" represents methyl or a methyl group, "Et" represents ethyl or an ethyl group, "Pr" represents propyl or a propyl group, and "Bu" represents a butyl or butyl group. Furthermore, the "i" accompanying the alkyl group name indicates iso, "n" indicates normal, "s" indicates secondary, and "t" indicates tertiary isomer structures. If an alkyl group is not accompanied by a symbol indicating an isomer structure, it indicates the normal structure. The substituent positions of metallocene compounds are determined according to IUPAC nomenclature as follows. In the general formula (1) below, the indenyl ligand is R 5 and R 11 2nd place, R 6 and R 12 3rd place, R 7 and R 13 4th place, R 8 and R 14 5th place, R 9 and R 15 6th place, R 10 and R 16 This is at position 7. The xylene skeleton of the crosslinking portion is assigned position numbers such that the two methylene groups at the ortho position are substituted at position 1 or 2, and the sum of the position numbers, including other substituents, is minimized. Specifically, R 1 or R 4 3rd or 6th, R 2 or R 3 They are in 4th or 5th place.

[0031] I. Metallocene Compounds The metallocene compound of the present invention is represented by the following general formula (1).

[0032] [ka]

[0033] [In general formula (1), M represents one of the transition metals Ti, Zr, or Hf. X 1 and X 2Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, a hydrocarbon group substituted with 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, a hydrocarbon group substituted with 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group substituted with 1 to 20 carbon atoms, R 1 ~R 16 Adjacent atoms or groups may be bonded to each other, forming a cyclic structure together with the atoms they are bonded to. However, R 1 , R 2 , R 3 and R 4 At least one of these represents an atom or group other than a hydrogen atom.

[0034] In general formula (1), M represents a transition metal of Ti, Zr, or Hf, preferably Zr or Hf, more preferably Zr.

[0035] In general formula (1), X 1 and X 2Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, a hydrocarbon group substituted with 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Specific examples of halogen atoms include, for instance, chlorine, bromine, iodine, and fluorine atoms.

[0036] Specific examples of hydrocarbon groups having 1 to 20 carbon atoms include alkyl or cycloalkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, octyl, cyclopropyl, cyclopentyl, and cyclohexyl groups; alkenyl groups such as vinyl, propenyl, butenyl, hexenyl, and cyclohexenyl groups; and alicyclic substituents such as cyclopentylmethyl and 2-cyclohexylethyl groups. Examples include aryl groups; monocyclic or fused ring aryl groups which may be substituted with saturated or unsaturated hydrocarbon groups such as phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 4-t-butylphenyl group, 3,5-di-t-butylphenyl group, 4-vinylphenyl group, 3-allylphenyl group, 4-(3-butenyl)phenyl group, naphthyl group, etc.; alkyl groups having aromatic substituents such as benzyl group, 2-phenylethyl group, etc.

[0037] Specific examples of hydrocarbon groups having 1 to 20 carbon atoms that contain an oxygen atom or a nitrogen atom include the following: Examples of groups containing oxygen atoms include hydrocarbon groups having ether bonds, carbonyl groups, ester bonds, heteroaryl groups, etc., such as alkoxyalkyl groups such as methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, t-butoxymethyl group, methoxyethyl group, ethoxyethyl group, 4-methoxybutyl group, 3-ethoxybutyl group, 6-methoxyhexyl group; 2-methoxyphenyl group, 3-methoxymethyl group Examples include alkoxy aromatic groups such as xyphenyl group, 4-methoxyphenyl group, and 2,4-dimethoxyphenyl group; oxo group-containing hydrocarbon groups such as acetyl group, 1-oxopropyl group, 1-oxo-n-butyl group, 2-methyl-1-oxopropyl group, 2,2-dimethyl-1-oxopropyl group, phenylacetyl group, diphenylacetyl group, and benzoyl group; and cyclic ether groups such as 2-furyl group, 2-methylfuryl group, 2-tetrahydrofuryl group, and 2-(5-methyl)furyl group. Examples of groups containing a nitrogen atom include hydrocarbon groups having amino groups, imino groups, nitrile groups, pyridyl groups, pyrrole groups, imidazole groups, pyrazole groups, and indole groups. For example, amino-substituted alkyl groups such as dimethylaminomethyl group, diethylaminomethyl group, di-i-propylaminomethyl group, bis(dimethylamino)methyl group, bis(di-i-propylamino)methyl group, (dimethylamino)(phenyl)methyl group, aminoethyl group, dimethylaminoethyl group, diethylaminoethyl group, 1-(methylimino)ethyl group, 1-(phenylimino)ethyl group, 1-[(phenylmethyl)imino]ethyl group, dimethylaminohexyl group, and amino-substituted aromatic groups such as 4-aminophenyl group and 4-dimethylaminophenyl group.

[0038] Specific examples of hydrocarbon group-substituted amino groups having 1 to 20 carbon atoms include dimethylamino group, diethylamino group, di-n-propylamino group, di-i-propylamino group, di-i-butylamino group, di-t-butylamino group, di-t-butylamino group, and diphenylamino group. Specific examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a t-butoxy group, a phenoxy group, and the like.

[0039] In general formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms. Specific examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group having (1 to 20 carbon atoms containing oxygen or nitrogen), the hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, and the alkoxy group having 1 to 20 carbon atoms are the same as the specific examples of the substituents of X 1 and X 2 described above, and can also be cited for R 1 to R 16 . Specific examples of hydrocarbon groups with 1 to 20 carbon atoms containing 1 to 6 silicon atoms include hydrocarbon groups substituted with 1 to 6 trialkylsilyl groups, where the total number of carbon atoms, including the alkylsilyl carbon atoms, is 1 to 20. More specifically, examples include alkylsilyl-substituted alkyl groups such as bis(trimethylsilyl)methyl group, bis(t-butyldimethylsilyl)methyl group, trimethylsilylethyl group, triethylsilylethyl group, and 2-trimethylsilylpropyl group; and alkylsilyl-substituted aromatic hydrocarbon groups such as 4-trimethylsilylphenyl group.

[0040] Specific examples of halogen-substituted hydrocarbon groups having 1 to 20 carbon atoms include halogenated alkyl groups such as bromomethyl, chloromethyl, trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 4-chlorobutyl, 3-fluorobutyl, and 4,4,4-trifluorobutyl; halogenated cycloalkyl groups such as 2-bromocyclopentyl, 2,3-dibromocyclopentyl, 2-bromo-3-iodocyclopentyl, 2,3-dibromocyclohexyl, and 2-chloro-3-iodocyclohexyl; halogenated aromatic groups such as 2-chlorophenyl, 4-chlorophenyl, 3,5-dichlorophenyl, and 2,3,4,5,6-pentafluorophenyl; and halogenated alkyl aromatic groups such as 4-trifluoromethylphenyl. Specific examples of hydrocarbon group-substituted silyl groups having 1 to 20 carbon atoms include trialkylsilyl groups, dialkylmonoarylsilyl groups, monoalkyldiarylsilyl groups, and triarylsilyl groups. Examples include alkylsilyl groups such as trimethylsilyl group, tri-t-butylsilyl group, di-t-butylmethylsilyl group, and t-butyldimethylsilyl group, and aromatic silyl groups such as triphenylsilyl group, diphenylmethylsilyl group, and phenyldimethylsilyl group.

[0041] The above R 1 ~R 16Among them, adjacent atoms or groups may bond to each other and, together with the atoms to which they are bonded, may form a cyclic structure. Examples of the cyclic structure formed include aromatic rings such as the benzene-1,2-yl group, and alicyclic 4- to 7-membered rings such as the cyclobutane-1,2-diyl group (cyclobutylidene group), cyclopentane-1,2-diyl group (cyclopentylidene group), and cyclohexane-1,2-diyl group (cyclohexylidene group). Substituent R on the orthoxylene skeleton which is the bridging part 1 , R 2 , R 3 and R 4 are preferably each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. However, in the general formula (1), at least one of R 1 , R 2 , R 3 and R 4 represents an atom or group other than a hydrogen atom, and two or more of them may be atoms or groups other than a hydrogen atom. By introducing an atom or group other than a hydrogen atom onto the orthoxylene skeleton, a metallocene compound excellent in solvent solubility and having sufficient ability as a catalyst component can be obtained.

[0042] As described above, the present invention does not exclude the introduction of substituents onto the indenyl ligand of the metallocene compound composed of an orthoxylene bisindenyl complex. Examples of the substituent on the indenyl ligand include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 3 to 20 carbon atoms containing an oxygen atom, a sulfur atom or a nitrogen atom, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms. When adjacent substituents are present on the indenyl ligand, they may bond to form a ring structure. When introducing substituents on an indenyl ligand, it is preferable that the substituents be small in size, from the viewpoint of minimizing the decrease in polymerization activity due to the shielding effect on the polymerization field. For example, fluorine atoms, chlorine atoms, methyl groups, ethyl groups, methoxy groups, ethoxy groups, trimethylsilylmethyl groups, methoxymethyl groups, chloromethyl groups, dichloromethyl groups, trichloromethyl groups, fluoromethyl groups, difluoromethyl groups, trifluoromethyl groups, trimethylsilyl groups, etc., are preferred.

[0043] Specific examples of metallocene compounds represented by general formula (1) include the following:

[0044] [Table 1-1]

[0045] [Table 1-2]

[0046] [Table 1-3]

[0047] [Table 1-4]

[0048] Metallocene compounds represented by general formula (1) can be produced using general synthesis methods for metallocene compounds. A general procedure involves synthesizing an indenyl lithium salt from indene and butyllithium, and then reacting two equivalents of this lithium salt with α,α'-dibromo-orthoxylene to synthesize α,α'-bis(1-indenyl)-orthoxylene, a ligand for metallocene. Subsequently, a lithium salt of the ligand is synthesized with butyllithium, and then reacted with zirconium tetrachloride to obtain metallocene. Methods for introducing substituents on the orthoxylene skeleton or indenyl ligands include synthesizing metallocene compounds using orthoxylene-based compounds and indene-based compounds having those substituents, or introducing substituents after the synthesis of the metallocene compound using known substitution reactions. In general formula (1), when synthesizing a compound in which substituents on the orthoxylene skeleton or indenyl ligands bond to each other to form a cyclic structure, or in which such cyclic structure further forms a polycyclic structure, a starting compound that already forms a monocyclic or polycyclic structure may be used, or the cyclic structure may be formed by ring-closing substituents during or at the final stage of synthesis. Furthermore, when synthesizing metallocene compounds represented by general formula (1), one can refer to Example 1 of Japanese Patent Application Publication No. 9-286812 and the synthesis example of compound 1a described in Journal of Organometallic Chemistry 535 (1997) 29-32.

[0049] II. Catalysts for Olefin Polymerization Metallocene compounds represented by general formula (1) are catalytically active components for olefin polymerization, and can be used as catalysts for olefin polymerization in combination with co-catalysts and supports. In the present invention, for example, an olefin polymerization catalyst containing the following components (A) and (B) as essential components can be used. • Component (A): Metallocene compound represented by the above general formula (1) • Component (B): A compound that reacts with component (A) to produce a cationic metallocene compound. Furthermore, in the present invention, for example, an olefin polymerization catalyst containing the following components (A), (B), and (C) as essential components can be used. • Component (A): Metallocene compound represented by the above general formula (1) • Component (B): A compound that reacts with component (A) to produce a cationic metallocene compound. • Component (C): Particulate carrier Furthermore, the above-mentioned catalyst for olefin polymerization may also contain an organoaluminum compound as component (D). Each component may use two or more different ingredients.

[0050] The metallocene compound represented by general formula (1) of component (A) is as described above. Components (B) and (C) are described below. 1. Ingredient (B) Component (B), that is, the compound that reacts with component (A) to produce a cationic metallocene compound, is a co-catalyst. For example, component (B) can be an organoaluminum oxy compound, a borane compound, a borate compound, or a layered silicate, as described later. Of these, organoaluminum oxy compounds are preferably used.

[0051] (1) Organoaluminum oxy compounds Organoaluminum oxy compounds are compounds that have Al-O-Al bonds in their molecules, and the number of Al-O-Al bonds is usually in the range of 1 to 100, preferably 1 to 50. Typically, organoaluminum oxy compounds containing a chain structure of -(O-Al)- units, such as those represented by formula (2-1) or formula (2-2) below, are used.

[0052] [ka]

[0053] [ka]

[0054] [In each of the above formulas, R 41 Each is independently a hydrogen atom or a hydrocarbon group, preferably a hydrocarbon group having 1 to 18 carbon atoms, more preferably an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, and R 41 At least a portion of it is a hydrocarbon group. p represents an integer between 0 and 40, preferably between 2 and 30.

[0055] Such organoaluminum oxy compounds are usually obtained by reacting an organoaluminum compound with water. The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon (solvent). Suitable inert hydrocarbons include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene; however, the use of aliphatic or aromatic hydrocarbons is preferred.

[0056] As the raw material organoaluminum compound, a compound represented by the following formula (3) can be used, but trialkylaluminum is preferred. Formula (3): R 41 t AlX 6 3-t [In formula (3), R 41 This is the same as equations (2-1) and (2-2) above, and X 6 [where 't' represents a hydrogen atom or a halogen atom, and 't' represents an integer between 1 and 3.]

[0057] The alkyl group of trialkylaluminum can be any of the following: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, octyl, decyl, or dodecyl group, but a methyl group is particularly preferred. Two or more of the above organoaluminum compounds can also be used in combination.

[0058] The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is preferably 0.25 / 1 to 1.2 / 1, particularly 0.5 / 1 to 1 / 1. The reaction temperature is usually in the range of -70 to 100°C, preferably -20 to 20°C. The reaction time is usually selected from 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As the water required for the reaction, not only plain water but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate, etc., and components that can generate water in the reaction system can be used.

[0059] Organoaluminum oxy compounds using trimethylaluminum as the raw material are called methylaluminoxane (MAO) and are particularly preferred. MAO can also be used as component (III) in a form containing unreacted trimethylaluminum. This unreacted trimethylaluminum is present at a concentration of 1 to 30 mol% relative to the total aluminum atoms of trimethylaluminum and methylaluminoxane. If the amount is too low, the MAO precipitates in the solution, making it difficult to use. If the amount of trimethylaluminum is too high, the risk of handling increases, making it difficult to use. Preferably, an MAO solution containing 10 to 15 mol% trimethylaluminum is preferable. Furthermore, if the concentration of MAO is too high, the risk of handling increases, and the MAO precipitates during storage, making it difficult to use. If the concentration is too low, safety and resistance to precipitation increase, but the containers and equipment required for handling become larger, resulting in economic disadvantages. Preferably, a concentration of 10 to 20% by weight of MAO is used. In addition, since MAO solutions tend to precipitate at room temperature, low-temperature storage below -10°C is preferred. Of course, two or more of the above-mentioned organoaluminum oxy compounds can be used in combination as the organoaluminum oxy compound, and a solution or dispersion of the organoaluminum oxy compound in the aforementioned inert hydrocarbon solvent may also be used.

[0060] (2) Borane compounds Examples of borane compounds include the following: triphenylborane, tri(o-tolyl)borane, tri(p-tolyl)borane, tri(m-tolyl)borane, tri(o-fluorophenyl)borane, tris(p-fluorophenyl)borane, tris(m-fluorophenyl)borane, tris(2,5-difluorophenyl)borane, tris(3,5-difluorophenyl)borane, tris(4-trifluoromethylphenyl)borane, tris(3,5-ditrifluoromethylphenyl)borane, tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, tris(perfluorobiphenyl)borane, tris(perfluoroanthryl)borane, and tris(perfluorobinaphthyl)borane.

[0061] Among these, the following compounds are preferred: tris(3,5-ditrifluoromethylphenyl)borane, tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, tris(perfluorobiphenyl)borane, tris(perfluoroantryl)borane, and tris(perfluorobinaphthyl)borane are more preferred. Among these, the following compounds are even more preferred: tris(2,6-ditrifluoromethylphenyl)borane, tris(pentafluorophenyl)borane, tris(perfluoronaphthyl)borane, and tris(perfluorobiphenyl)borane.

[0062] (3) Borate compounds One example of a borate compound is the compound represented by the following formula (4). Formula (4): [L 6 -H] + [BR 42 R 43 X 7 X 7’ ] -

[0063] In formula (4), L 6H is a neutral Lewis base, and H is a hydrogen atom, [L 6 -H] is a Brønsted acid such as ammonium, anilinium, or phosphonium. Examples of ammonium compounds include trialkyl-substituted ammonium compounds such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, and tri(n-butyl)ammonium, as well as dialkylammonium compounds such as di(n-propyl)ammonium and dicyclohexylammonium. Examples of anilinium include N,N-dimethylanilinium, N,N-diethylanilinium, and N,N-2,4,6-pentamethylanilinium, which are all N,N-dialkylanilinium species. Furthermore, examples of phosphoniums include triarylphosphoniums and trialkylphosphoniums such as triphenylphosphonium, tributylphosphonium, tri(methylphenyl)phosphonium, and tri(dimethylphenyl)phosphonium.

[0064] Also, in equation (4), R 42 and R 43 These are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16, carbon atoms, which may be linked to each other by a crosslinking group. Preferred substituents for the substituted aromatic hydrocarbon groups are alkyl groups such as methyl, ethyl, propyl, and isopropyl groups, and halogens such as fluorine, chlorine, bromine, and iodine. Furthermore, X 7 and X 7’ These are, independently, a hydrogen atom, a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, and a substituted hydrocarbon group containing 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by halogen atoms.

[0065] Specific examples of compounds represented by the above general formula (4) include, for example, the following compounds: tributylammonium tetra(pentafluorophenyl) borate, tributylammonium tetra(2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra(3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra(2,6-difluorophenyl) borate, tributylammonium tetra(perfluoronaphthyl) borate, dimethylanilinium tetra(pentafluorophenyl) borate, dimethylanilinium tetra(2,6-ditrifluoromethylphenyl) borate, dimethylanilinium tetra(3 ,5-Ditrifluoromethylphenyl) borate, Dimethylanilinium tetra(2,6-Difluorophenyl) borate, Dimethylanilinium tetra(perfluoronaphthyl) borate, Triphenylphosphonium tetra(pentafluorophenyl) borate, Triphenylphosphonium tetra(2,6-Ditrifluoromethylphenyl) borate, Triphenylphosphonium tetra(3,5-Ditrifluoromethylphenyl) borate, Triphenylphosphonium tetra(2,6-Difluorophenyl) borate, Triphenylphosphonium tetra(perfluoronaphthyl) borate, Trimethylammonium tetra(2,6-Ditrifluoromethylphenyl) Borate, triethylammonium tetra(pentafluorophenyl) borate, triethylammonium tetra(2,6-ditrifluoromethylphenyl) borate, triethylammonium tetra(perfluoronaphthyl) borate, tripropylammonium tetra(pentafluorophenyl) borate, tripropylammonium tetra(2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra(perfluoronaphthyl) borate, di(1-propyl)ammonium tetra(pentafluorophenyl) borate, dicyclohexylammonium tetraphenyl borate.

[0066] Among these, the following compounds are preferred: tributylammonium tetra(pentafluorophenyl) borate, tributylammonium tetra(2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra(3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra(perfluoronaphthyl) borate, dimethylanilinium tetra(pentafluorophenyl) borate, dimethylanilinium tetra(2,6-ditrifluoromethylphenyl) borate, dimethylanilinium tetra(3,5-ditrifluoromethylphenyl) borate, and dimethylanilinium tetra(perfluoronaphthyl) borate.

[0067] A second example of a borate compound is the compound represented by the following formula (5). Formula (5): [L 7 ] + [BR 42 R 43 X 7’ X 7’ ] -

[0068] In formula (5), L 7 Examples include carbocations, methyl cations, ethyl cations, propyl cations, isopropyl cations, butyl cations, isobutyl cations, t-butyl cations, pentyl cations, tropinium cations, benzyl cations, trityl cations, sodium cations, protons, etc. Also, R 42 , R 43 , X 7 and X 7’ This is the same as the definition in equation (4) above.

[0069] Specific examples of compounds represented by formula (5) above include the following: trityltetraphenyl borate, trityltetra(o-tolyl)borate, trityltetra(p-tolyl)borate, trityltetra(m-tolyl)borate, trityltetra(o-fluorophenyl)borate, trityltetra(p-fluorophenyl)borate, trityltetra(m-fluorophenyl)borate, trityltetra(3,5-difluorophenyl)borate, trityltetra(pentafluorophenyl)borate, trityltetra(2,6-ditrifluoromethylphenyl)borate, trityltetra(3,5-ditrifluoromethylphenyl)borate, trityltetra(perfluoronaphthyl)borate, tropiniumtetraphenyl borate, tropiniumtetra(o-tolyl)borate, tropiniumtetra(p-tolyl)borate, tropiniumtetra(m- Tropium(Tryl)borate, Tropium(o-fluorophenyl)borate, Tropium(p-fluorophenyl)borate, Tropium(m-fluorophenyl)borate, Tropium(3,5-difluorophenyl)borate, Tropium(pentafluorophenyl)borate, Tropium(2,6-ditrifluoromethylphenyl)borate, Tropium(3,5-ditrifluoro Methylphenyl borate, tropinium tetra(perfluoronaphthyl) borate, NaBPh4, NaB(o-CH3-Ph)4, NaB(p-CH3-Ph)4, NaB(m-CH3-Ph)4, NaB(oF-Ph)4, NaB(pF-Ph)4, NaB(mF-Ph)4, NaB(3,5-F2-Ph)4, NaB(C6F5)4, NaB(2,6-(CF3)2-Ph)4, NaB(3,5-(CF3)2-Ph)4, NaB(C 10 F7)4, HBPh4·(ET2O)2, HB(3,5-F2-Ph)4·(ET2O)2, HB(C6F5)4·(ET2O)2, HB(2,6-(CF3)2-Ph)4·(ET2O)2, HB(3,5-(CF3)2-Ph)4·(ET2O)2, HB(C 10 H7)4·(ET2O)2.

[0070] Among these, the following compounds are preferred: trityltetra(pentafluorophenyl)borate, trityltetra(2,6-ditrifluoromethylphenyl)borate, trityltetra(3,5-ditrifluoromethylphenyl)borate, trityltetra(perfluoronaphthyl)borate, tropiniumtetra(pentafluorophenyl)borate, tropiniumtetra(2,6-ditrifluoromethylphenyl)borate, tropiniumtetra(3,5-ditrifluoromethylphenyl)borate, tropiniumtetra(perfluoronaphthyl)borate, NaB(C6F5)4, NaB(2,6-(CF3)2-Ph)4, NaB(3,5-(CF3)2-Ph)4, NaB(C 10 F7)4, HB(C6F5)4·(ET2O)2, HB(2,6-(CF3)2-Ph)4·(ET2O)2, HB(3,5-(CF3)2-Ph)4·(ET2O)2, HB(C 10 H7)4·(ET2O)2.

[0071] Among these, the following compounds are even more preferred: trityltetra(pentafluorophenyl)borate, trityltetra(2,6-ditrifluoromethylphenyl)borate, tropiniumtetra(pentafluorophenyl)borate, tropiniumtetra(2,6-ditrifluoromethylphenyl)borate, NaB(C6F5)4, NaB(2,6-(CF3)2-Ph)4, HB(C6F5)4·(ET2O)2, HB(2,6-(CF3)2-Ph)4·(ET2O)2, HB(3,5-(CF3)2-Ph)4·(ET2O)2, HB(C 10 H7)4·(ET2O)2.

[0072] Furthermore, as component (B), a mixture of the aforementioned organoaluminum oxy compound and the above-mentioned borane compound or borate compound may also be used. In addition, two or more of the above-mentioned borane compounds or borate compounds may be used in mixture form.

[0073] 2.Component (C) Component (C), i.e., the fine particle carrier, may be an inorganic carrier, a particulate polymer carrier, or a mixture thereof. The inorganic carrier can be a metal, a metal oxide, a metal chloride, a metal carbonate, a carbonaceous material, or a mixture thereof. Suitable metals that can be used as inorganic carriers include, for example, iron, aluminum, and nickel.

[0074] Furthermore, examples of metal oxides include single or complex oxides of elements from groups 1 to 14 of the periodic table. For example, various natural or synthetic single or complex oxides such as SiO2, Al2O3, MgO, CaO, B2O3, TiO2, ZrO2, Fe2O3, Al2O3·MgO, Al2O3·CaO, Al2O3·SiO2, Al2O3·MgO·CaO, Al2O3·MgO·SiO2, Al2O3·CuO, Al2O3·Fe2O3, Al2O3·NiO, and SiO2·MgO can be cited. Here, the above formulas represent only the composition, not the molecular formula, and the structure and component ratio of the complex oxides used in the present invention are not particularly limited. In addition, the metal oxides used in the present invention may absorb small amounts of moisture and may contain small amounts of impurities.

[0075] As metal chlorides, alkali metal and alkaline earth metal chlorides are preferred, and specifically MgCl2 and CaCl2 are particularly preferred. As metal carbonates, alkali metal and alkaline earth metal carbonates are preferred, and specifically, magnesium carbonate, calcium carbonate, and barium carbonate are examples. Examples of carbonaceous materials include carbon black and activated carbon. All of the inorganic supports described above can be suitably used in the present invention, but metal oxides, silica, and alumina are preferred, and silica is even more preferred. As for silica, it is preferable to use small-particle silica with an average particle size of about 10 μm to 150 μm. Here, the average particle size is the value expressed as the median diameter from data expressed on a volume basis using a commonly used laser diffraction measurement method.

[0076] These inorganic supports are usually calcined at 200°C to 800°C, preferably 400°C to 600°C, in air or inert gas such as nitrogen or argon, to adjust the amount of surface hydroxyl groups to 0.8 mmol / g to 1.5 mmol / g before use. While there are no particular restrictions on the properties of these inorganic supports, typically the average particle size is 5 μm to 200 μm, preferably 10 μm to 150 μm, the average pore size is 20 Å to 1000 Å, preferably 50 Å to 500 Å, and the specific surface area is 150 m². 2 / g~1000m 2 / g, preferably 200m 2 / g~700m 2 / g, pore volume is 0.3 cm³ 3 / g~2.5cm 3 / g, preferably 0.5cm 3 / g~2.0cm 3 / g, apparent specific gravity is 0.20 g / cm³ 3 ~0.50g / cm 3 Preferably 0.25 g / cm³ 3 ~0.45g / cm 3 It is preferable to use an inorganic carrier having the following properties.

[0077] The inorganic supports described above can, of course, be used as is, but they can also be used after being pre-treated by contacting them with organoaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum, and diisobutylaluminum hydride, or with organoaluminum oxy compounds containing Al-O-Al bonds.

[0078] III. Preparation of catalysts for olefin polymerization The olefin polymerization catalyst of the present invention can be prepared by contacting component (A), which is a metallocene compound represented by general formula (1) as at least a catalytically active component, with component (B), which is a co-catalyst, preferably by contacting component (C), which is a fine particle carrier, in addition to components (A) and (B), and further by contacting other components as needed. The method of contacting each component is not particularly limited, and for example, the following methods can be arbitrarily adopted.

[0079] Method (1): After bringing component (A) and component (B) into contact, bring component (C) into contact. Method (2): After bringing component (A) and component (C) into contact, bring component (B) into contact. Method (3): After bringing component (B) and component (C) into contact, bring component (A) into contact. Of these contact methods, methods (1) and (3) are preferred, and method (1) is the most preferred.

[0080] In any contact method, the components are typically brought into contact with each other under stirring or without stirring, in an inert atmosphere such as nitrogen or argon, in the presence of liquid inert hydrocarbons such as aromatic hydrocarbons (usually with 6 to 12 carbon atoms) including benzene, toluene, xylene, and ethylbenzene, and aliphatic or alicyclic hydrocarbons (usually with 5 to 12 carbon atoms) including heptane, hexane, decane, dodecane, and cyclohexane. This contact is preferably carried out at a temperature of -100°C to 200°C, preferably -50°C to 100°C, and more preferably 0°C to 50°C, for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, and more preferably 30 minutes to 12 hours.

[0081] Furthermore, when components (A), (B), and (C) come into contact, both aromatic hydrocarbon solvents in which certain components are soluble or sparingly soluble, and aliphatic or alicyclic hydrocarbon solvents in which certain components are insoluble or sparingly soluble, can be used.

[0082] When the contact reactions between components are carried out in steps, the solvent used in the preceding step may be used directly as the solvent for the subsequent contact reaction without removing it. Alternatively, after the initial contact reaction using a soluble solvent, a liquid inert hydrocarbon in which certain components are insoluble or sparingly soluble (for example, aliphatic hydrocarbons, alicyclic hydrocarbons, or aromatic hydrocarbons such as pentane, hexane, decane, dodecane, cyclohexane, benzene, toluene, and xylene) may be added to recover the desired product as a solid, or after removing part or all of the soluble solvent by means of drying or other means to obtain the desired product as a solid, the subsequent contact reaction of this desired product may be carried out using one of the above-mentioned inert hydrocarbon solvents. The present invention does not prevent the contact reactions of each component from being carried out multiple times.

[0083] In the present invention, the proportions of component (A), component (B), and component (C) used are not particularly limited, but the following ranges are preferred.

[0084] When an organoaluminum oxy compound is used as component (B), the molar ratio of aluminum atoms in the organoaluminum oxy compound to the transition metal (M) contained in component (A) (A l / M) is usually in the range of 1 to 100,000, preferably 5 to 1,000, and more preferably 50 to 500. Furthermore, when using borane compounds or borate compounds, the molar ratio (B / M) of boron atoms to the transition metal (M) contained in component (A) is usually selected within the range of 0.01 to 100, preferably 0.1 to 50, and more preferably 0.2 to 10. Furthermore, when using a mixture of an organoaluminum oxy compound and a borane compound and / or a borate compound as component (B), it is desirable that the proportions of Al and B used for each compound in the mixture be the same as those described above, relative to the transition metal (M) contained in component (A).

[0085] The amount of component (C), which is a fine particle carrier, used is such that the transition metal contained in component (A) is 0.0001 mmol to 5 mmol per gram of component (C), preferably 0.001 mmol to 0.5 mmol, and more preferably 0.01 mmol to 0.1 mmol.

[0086] An olefin polymerization catalyst can be obtained by bringing components (A), (B), and (C) into contact with each other using any of the contact methods (1) to (3) described above. However, after the contact step, a washing step may be performed to remove unreacted substances and unwanted products, and then the solvent may be removed. In the washing process, methods such as allowing the olefin polymerization catalyst to settle, then removing the unnecessary supernatant, adding a new solvent and stirring to homogenize it, repeating the stirring and homogenization process, or washing using a filter device are employed. The solvent used in the washing process is one that can be used in contact with components (A) to (C). The solvent can also be changed during the washing process. For the solvent removal process, methods such as distillation, in which the solvent is evaporated at a pressure corresponding to the boiling point of the solvent, or vaporization, in which the solvent is vaporized by a stream of dry inert gas, can be used. It is desirable to remove the solvent under normal pressure or reduced pressure, at 0°C to 200°C, preferably 20°C to 150°C, for 1 minute to 50 hours, preferably 10 minutes to 10 hours. The olefin polymerization catalyst obtained after the washing process can be handled or stored in slurry form, and the olefin polymerization catalyst obtained in the solvent removal process can be handled or stored as a powdered solid catalyst.

[0087] When using method (1) of the above contact methods (1) to (3), the catalyst for olefin polymerization can be prepared by following the steps 1 to 3 below. Step 1: Mix component (A) with a hydrocarbon solvent to prepare a complex solution a in which component (A) is completely dissolved. Step 2: Mix the complex solution a obtained in Step 1 with component (B) to prepare a mixed solution b. Step 3: Mix the mixture b obtained in Step 2 with component (C) to prepare slurry c. Since metallocene compounds represented by general formula (1) have excellent solvent solubility, a highly concentrated, completely dissolved complex solution can be prepared in step 1 above. Here, "completely dissolved complex solution" means a complex solution in which there are no undissolved components. Furthermore, it can be determined that there are no undissolved components if the insoluble portion of component (A) is recognized as being 1% or less by weight. An insoluble portion of 1% or less by weight refers to the following state: The complex solution is filtered using a glass filter (filter mesh G3) under inert gas conditions, and then, in order to remove the solvent adhering to the filter, it is dried under reduced pressure for another 30 minutes using a vacuum pump until no further weight loss is observed. The temperature at this time is not particularly restricted as long as it is a temperature and degree of reduced pressure at which the hydrocarbon solvent used can be removed under reduced pressure, and the complex does not decompose. After this reduced-pressure drying, the weight of the complex remaining on the filter is 1% or less of the weight of the introduced complex. From the viewpoint of ensuring sufficient concentration without any undissolved residue, the concentration of component (A) in the complex solution a is preferably 2.5 mmol / L or more and 100 mmol / L or less, and more preferably 3.0 mmol / L or more and 50 mmol / L or less.

[0088] Component (A) is determined by the solubility (using an internal standard) obtained by the measurement method described later. 1 The solubility in toluene solvent (measured by 1H-NMR) may be 2.0 mmol / L to 2,500 mmol / L, preferably 2.5 mmol / L to 1,000 mmol / L, and more preferably 3.0 mmol / L to 500 mmol / L. Having the solubility within this range allows for the avoidance of using large amounts of solvent or environmentally harmful solvents in the synthesis process of component (A). Furthermore, in the production process of olefin polymerization catalysts using component (A), particularly in the production of multi-supported catalysts combining multiple metallocene compounds, it is possible to produce catalysts with stable catalytic performance without using large amounts of solvent.

[0089] Furthermore, the slurry c obtained in step 3 can be dried in step 4 to obtain a solid catalyst. The metallocene compound represented by general formula (1) exhibits excellent solvent solubility and possesses sufficient catalytic activity. Therefore, by using this metallocene compound, a highly concentrated, completely dissolved complex solution can be prepared, and a large amount of the metallocene compound, which possesses sufficient catalytic activity, can be uniformly supported on a carrier. Consequently, a solid catalyst with high polymerization activity can be obtained.

[0090] Furthermore, the olefin polymerization catalyst of the present invention can also be obtained by the following method. Method (4): Component (A) and component (C), which is a fine particle carrier, are brought into contact to remove the solvent, and this is used as a solid catalyst component. This is then brought into contact with component (B), which is a co-catalyst, under polymerization conditions. Method (5): The co-catalyst component (B) and the fine particle carrier component (C) are brought into contact to remove the solvent, and this is converted into a solid catalyst component, which is then brought into contact with the catalytically active component (A) under polymerization conditions. In the case of methods (4) and (5) described above, the same conditions as described above can be adopted for the component ratio, contact conditions, and solvent removal conditions.

[0091] Furthermore, layered silicates can be used as a component that serves as both a co-catalyst (B) and a fine particle carrier (C). Layered silicates are silicate compounds that have a crystalline structure in which planes formed by ionic bonds, etc., are stacked parallel to each other with weak bonding forces. Most layered silicates occur naturally mainly as the main component of clay minerals, but these layered silicates are not limited to natural products and may also be artificially synthesized. Among these, smectites such as montmorillonite, sauconite, bidelite, nontronite, saponite, hectorite, stevensite, bentonite, and teniolite, as well as vermiculites and micas, are preferred.

[0092] Generally, natural products are often non-ion-exchangeable (non-swelling), and in such cases, it is preferable to perform a treatment to impart ion-exchangeability (or swelling) to achieve desirable ion-exchangeability (or swelling). Among such treatments, the following chemical treatments are particularly preferred. Here, chemical treatment can be either a surface treatment to remove impurities adhering to the surface or a treatment that affects the crystal structure and chemical composition of the layered silicate. Specifically, these include (a) acid treatment using hydrochloric acid, sulfuric acid, etc., (b) alkali treatment using NaOH, KOH, N₂H₃, etc., (c) salt treatment using salts consisting of a cation containing at least one atom selected from groups 2 to 14 of the periodic table and at least one anion selected from the group consisting of a halogen atom or an anion derived from an inorganic acid, and (d) organic treatment using alcohols, hydrocarbon compounds, formamide, aniline, etc. These treatments may be performed individually or in combination of two or more treatments.

[0093] The particle properties of the layered silicate can be controlled by grinding, granulation, particle separation, fractionation, etc., at any point before, during, or after any of the processes. The method can be any purposeful method. In particular, examples of granulation methods include spray granulation, tumbling granulation, compression granulation, agitation granulation, briquetting, compacting, extrusion granulation, fluid bed granulation, emulsification granulation, and liquid granulation. Of the above, spray granulation, tumbling granulation, and compression granulation are particularly preferred granulation methods.

[0094] While the layered silicates described above can certainly be used as is, they can also be used in combination with organoaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, and diisobutylaluminum hydride, as well as organoaluminum oxy compounds containing Al-O-Al bonds.

[0095] To support component (A), which is a catalytically active component, on a layered silicate, component (A) and the layered silicate may be brought into contact with each other, or component (A), an organoaluminum compound or organoaluminum oxy compound, and the layered silicate may be brought into contact with each other. The method of contact between each component is not particularly limited, and for example, the following methods can be arbitrarily adopted. Method (6): After contacting component (A) with an organoaluminum compound or organoaluminum oxy compound, the component is then brought into contact with a layered silicate carrier. Method (7): After bringing component (A) into contact with a layered silicate carrier, it is brought into contact with an organoaluminum compound or an organoaluminum oxy compound. Method(8): After bringing an organoaluminum compound or organoaluminum oxy compound into contact with a layered silicate carrier, it is brought into contact with component (A).

[0096] Of these contact methods, methods (6) and (8) are preferred. In any of the contact methods, the components are typically brought into contact with each other under stirring or without stirring in an inert atmosphere such as nitrogen or argon, in the presence of liquid inert hydrocarbons such as aromatic hydrocarbons (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene, and ethylbenzene, and aliphatic or alicyclic hydrocarbons (usually having 5 to 12 carbon atoms) such as heptane, hexane, decane, dodecane, and cyclohexane. When supporting component (A) on a layered silicate, the methods for supporting, solvent washing, and solvent removal can be the same as those for the inorganic support described above.

[0097] The ratio of component (A), which is the catalytically active component, to the organoaluminum compound or organoaluminum oxy compound and the layered silicate support is not particularly limited, but the following ranges are preferred. The amount of component (A) supported is such that, per gram of layered silicate carrier, the transition metal (M) contained in component (A) is 0.0001 mmol to 5 mmol, preferably 0.001 mmol to 0.5 mmol, and more preferably 0.01 mmol to 0.1 mmol. Furthermore, when using organoaluminum compounds or organoaluminum oxy compounds, the molar ratio (Al / M) of Al atoms contained in the organoaluminum compound or organoaluminum oxy compound to the transition metal (M) contained in component (A) is preferably in the range of 0.01 to 100, more preferably 0.1 to 50, and even more preferably 0.2 to 10.

[0098] IV. Prepolymerization of catalysts for olefin polymerization The olefin polymerization catalyst thus obtained may undergo prepolymerization in or outside the polymerization tank in the presence of olefins. Olefins are hydrocarbons containing at least one carbon-carbon double bond, and examples include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, and divinylbenzene, but there are no particular restrictions on the type, and mixtures of these with other olefins may be used. Preferably, ethylene and propylene are used. More preferably, ethylene is used.

[0099] The method of supplying olefins during prepolymerization can be any method, such as supplying the olefins to the reaction vessel at a constant rate or under constant pressure, a combination of these methods, or by introducing stepwise changes. The prepolymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours. The amount of prepolymerization is preferably 0.01 to 100 parts by weight, and more preferably 0.1 to 50 parts by weight, of the prepolymerized polymer per 1 part by weight of the polyolefin polymerization catalyst. After prepolymerization is complete, the catalyst can be used as is, depending on its intended use, but drying may be performed if necessary.

[0100] The prepolymerization temperature is not particularly limited, but is preferably 0°C to 100°C, more preferably 10°C to 70°C, particularly preferably 20°C to 60°C, and even more preferably 30°C to 50°C. Below this range, the reaction rate may decrease or the activation reaction may not proceed, which can be detrimental. Above this range, the prepolymerized polymer may dissolve, the prepolymerization rate may be too fast and the particle properties may deteriorate, or the active sites may be deactivated due to side reactions, which can be detrimental.

[0101] Prepolymerization can and is preferable to be carried out in a liquid such as an organic solvent. There are no particular restrictions on the concentration of the solid catalyst during prepolymerization, but it is preferably 50 g / L or more, more preferably 60 g / L or more, and particularly preferably 70 g / L or more. A higher concentration leads to more active component (A) and results in a highly active catalyst.

[0102] Furthermore, it is possible to include polymers such as polyethylene, polypropylene, and polystyrene, as well as inorganic oxide solids such as silica and titania, in the contact mixture during or after the contact between the olefin polymerization catalyst and the olefin.

[0103] The catalyst may be dried after prepolymerization. There are no particular restrictions on the drying method, but examples include drying under reduced pressure, heating, and drying by circulating a drying gas. These methods may be used individually or in combination of two or more methods. During the drying process, the catalyst may be stirred, vibrated, or allowed to flow, or it may be left to stand.

[0104] V. Polymerization of olefins The olefin polymerization catalyst obtained by the present invention can be used for the polymerization of olefins alone or for copolymerization of the olefin with other comonomers, and in particular for the homopolymerization of ethylene or for copolymerization of ethylene with propylene or α-olefins. Polymerizable olefins are preferably those with 2 to 20 carbon atoms, specifically including ethylene, propylene, 1-butene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl-1,7-octadiene, cyclopentene, norbornene, and ethylidenenorbornene. Preferably, the olefins have 2 to 8 carbon atoms.

[0105] In copolymerization, as the comonomer, an olefin other than the main component olefin can be selected and used from among the olefins listed above. When producing ethylene copolymers, it is preferable to use propylene and α-olefins having 4 to 8 carbon atoms as olefin comonomers, and it is even more preferable to use α-olefins having 4 to 6 carbon atoms.

[0106] Any polymerization method can be employed as long as the catalyst component and each monomer come into efficient contact. Specifically, slurry polymerization using an inert solvent, a method using propylene as the solvent without substantially using an inert solvent, solution polymerization, or a gas-phase method that keeps each monomer in gaseous form without substantially using a liquid solvent can be employed. Continuous polymerization, batch polymerization, or prepolymerization methods can also be applied. Among these, slurry polymerization is preferred. Furthermore, a multi-step polymerization method is also applicable, in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, and polymerization temperature are different for two or more stages. In slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as isobutane, hexane, heptane, pentane, cyclohexane, benzene, and toluene, either alone or in mixtures, are used as polymerization solvents. The polymerization temperature is 0°C to 150°C, and hydrogen can be used as an auxiliary molecular weight modifier. The polymerization pressure is preferably 0 MPa to 200 MPa, more preferably 0 MPa to 6 MPa. In gas-phase polymerization, ethylene or comonomers are polymerized in a reactor where a gaseous flow of ethylene or comonomers is introduced, circulated, or recirculated. Polymerization conditions are generally a temperature of 0°C to 250°C and a pressure of atmospheric pressure to 10 MPa. Polymerization times are typically between 5 minutes and 10 hours. In copolymerization, the relative amounts of each monomer in the reaction system do not need to remain constant over time. It is convenient to supply each monomer in a constant mixing ratio, and it is also possible to change the mixing ratio of the supplied monomers over time. Furthermore, it is possible to add any of the monomers in separate portions, taking into account the copolymerization reaction ratio.

[0107] Generally, when polymerizing ethylene-based polymers, it is possible to use antistatic agents such as Stadis or STATSAFE, manufactured by Innospec (distributed by Maruwa Bussan), to suppress the static adhesion of the polymer to the polymerization reactor. Antistatic agents such as Stadis and STATSAFE can also be added to the polymerization reactor by pumping after being diluted in an inert hydrocarbon medium. Methods of addition include adding it to the olefin polymerization catalyst in advance or adding it to the polymerization reactor. In the case of slurry polymerization, the amount added is preferably 0.1 ppm to 500 ppm relative to the solvent, and more preferably 1 ppm to 50 ppm. In the case of gas-phase polymerization, the amount added is preferably 1 ppm to 500 ppm relative to the amount of ethylene polymer produced per unit time, and more preferably 10 ppm to 100 ppm.

[0108] The molecular weight of the resulting polymer can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, but molecular weight can be adjusted more effectively by adding hydrogen to the polymerization reaction system.

[0109] Furthermore, components for removing moisture, so-called scavengers, may be added to the polymerization system. Suitable scavengers include organoaluminum compounds such as trimethylaluminum, triethylaluminum, and triisobutylaluminum; the aforementioned organoaluminum oxy compounds; modified organoaluminum compounds containing branched alkyl groups; organozinc compounds such as diethylzinc and dibutylzinc; organomagnesium compounds such as diethylmagnesium, dibutylmagnesium, and ethylbutylmagnesium; and greener compounds such as ethylmagnesium chloride and butylmagnesium chloride. Among these, triethylaluminum, triisobutylaluminum, and ethylbutylmagnesium are preferred, with triethylaluminum being particularly preferred. [Examples]

[0110] The present invention will be described in more detail in the following examples and comparative examples, but the present invention is not limited thereto. In the examples, the catalyst synthesis and polymerization steps were all carried out under a purified nitrogen atmosphere, and the solvent used was dehydrated and purified using molecular sieves such as 4A and 13X (trade names, manufactured by Union Showa Co., Ltd.).

[0111] 1. Measurement and Evaluation Methods (1) Measurement of the solubility of metallocene compounds in toluene The toluene solubility of the synthesized metallocene compound is, 1 The measurement was performed by 1H-NMR. Deuterated toluene was used as the measurement solvent, and 2,3,5,6-tetrabromo-p-xylene was used as the internal standard. A deuterated toluene solution of 2,3,5,6-tetrabromo-p-xylene of known concentration was prepared, and 0.6 ml of the deuterated toluene solution of 2,3,5,6-tetrabromo-p-xylene and a small amount of metallocene compound (enough to leave some residue) were added to a φ5 mm NMR sample tube, and sonication was performed at 25°C for 30 minutes. After confirming that a small amount of residue remained, the measurement conditions described below were used. 1 1H-NMR measurements were performed. The toluene solubility (unit: μmol / mL) of the metallocene compound was calculated from the relative integral values ​​of the obtained spectra of the metallocene compound and the internal standard. Equipment: JEOL Ltd. JNM-ECS400 Measurement temperature: 25℃ Pulse repetition time: 16 seconds Total: 64 times

[0112] (2) MFR (190℃, 2.16kg load) MFR was measured in accordance with JIS K6760, under conditions of a temperature of 190°C and a load of 2.16 kg. (3) Density Density was measured in accordance with JIS K6922-1,2:1997.

[0113] (4) Measurement of molecular weight Mw and molecular weight distribution (Mw / Mn) Gel permeation chromatography (GPC) was performed under the following conditions, and the number-average molecular weight (Mn) and weight-average molecular weight (Mw) were measured by converting the retention volume to molecular weight, and the molecular weight distribution (Mw / Mn) was calculated. [GPC equipment, measurement conditions] Equipment: Waters GPC (ALC / GPC 150C) Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm) Columns: Showa Denko AD806M / S (3 pieces) Mobile phase solvent: o-dichlorobenzene (ODCB) Measurement temperature: 140℃ Flow rate: 1.0ml / min Injection amount: 0.2ml [Sample preparation] The sample was dissolved in ODCB (containing 0.5 mg / mL of BHT) at 140°C for approximately 1 hour to prepare a sample solution with a concentration of 1 mg / mL. [Conversion from holding capacity to molecular weight] The conversion from holding capacity to molecular weight was performed using a calibration curve prepared in advance using standard polystyrene. The standard polystyrene used was the following brands manufactured by Tosoh Corporation: F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, and A1000. Calibration curves are created by injecting 0.2 mL of a solution of each standard polystyrene dissolved in ODCB (containing 0.5 mg / mL of BHT) so that the concentration becomes 0.5 mg / mL. The calibration curves are approximated using a cubic equation obtained by the least squares method. The viscosity formula [η] = K × Mα used for conversion to molecular weight is as follows. PS: K = 1.38 × 10 -4 α=0.7 PE:K = 3.92 × 10 -4 , α=0.733 PP:K = 1.03 × 10 -4 α = 0.78

[0114] (5) Measurement of comonomer content [Sample preparation] 200 mg of the sample was placed in 2.4 ml of ODCB / deuterated bromide benzene (C6D5Br) = 2 / 1 (volume ratio) and hexamethyldisiloxane, a reference substance for chemical shifts, in an NMR sample tube with an inner diameter of 10 mmφ. After purging with nitrogen, the tube was sealed and uniformly dissolved using a block heater at 150°C. NMR measurements were performed using a Bruker Japan AV400 NMR spectrometer equipped with a 10 mmφ cryoprobe. For the quantification of comonomer content, 13 1C-NMR was used. 13 The 1C-NMR measurement conditions were: sample temperature 120°C, pulse angle 45°, pulse interval 27.5 seconds, and integration count 512 or more times. The measurement was performed using the proton broadband decoupling method. The chemical shift is hexamethyldisiloxane. 13 Set the C signal to 1.98 ppm, and the other 13 The chemical shift of the signal due to C was based on this. The ethylene-1-hexene copolymer obtained under the above measurement conditions 13The hexene content (mol%) was determined using the following formula based on the 1C-NMR spectrum. Hexene content: C6(mol%)=I(H)×100 / [I(H)+I(E)] Ethylene content: C2 (mol%) = I(E) × 100 / [I(H) + I(E)] Here, I(H) and I(E) are quantities represented by the following equations, respectively. I(H) = I 23.6~23.0 I(E) = (I 24.6~24.4 -I 27.5~26.9 +I 32.0~28.0 ) / 2+I 35.2~34.3 / 4

[0115] 2.Materials used [Synthesis of metallocene compounds] (1) Synthesis of metallocene compound A: meso-4,5-dimethyl-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (1-1) Synthesis of 1,2-bis(chloromethyl)-4,5-dimethylbenzene In a 500 ml flask, 10.00 g (0.09419 mol) of o-xylene and 94.20 ml (0.9487 mol) of concentrated hydrochloric acid were added and cooled to 0°C. 8.55 g (0.0377 mol) of 1-butyl-3-methylimidazolium tetrafluoroborate and 8.56 g (0.283 mol) of paraformaldehyde were added, and the mixture was stirred at 70°C for 12 hours. Again, 94.20 ml (0.9487 mol) of concentrated hydrochloric acid and 2.85 g (0.0942 mol) of paraformaldehyde were added, and the mixture was stirred at 70°C for another 12 hours. The reaction mixture was concentrated by vacuum distillation, 200 ml of distilled water was added, and the mixture was extracted three times with 200 ml of dichloromethane. The resulting organic phase was washed with 200 ml of distilled water and dried over anhydrous sodium sulfate. The sodium sulfate was filtered, the solvent was removed by reduced pressure distillation, and the solution was purified using a silica gel column (petroleum ether) to obtain 18.00 g (94% yield) of 1,2-bis(chloromethyl)-4,5-dimethylbenzene as a white powder.

[0116] (1-2) Synthesis of 1,2-bis(1-indenylmethyl)-4,5-dimethylbenzene In a 500 ml flask, 17.16 g (0.1477 mol) of indene and 200 ml of tetrahydrofuran (THF) were added and cooled to -78°C. 55.14 ml (0.1379 mol) of n-butyllithium / n-hexane solution (2.5 M) was added dropwise, and the mixture was stirred for 2 hours while returning to room temperature. The mixture was cooled again to -78°C, and 10.00 g (0.04923 mol) of 1,2-bis(chloromethyl)-4,5-dimethylbenzene in 50 ml of THF solution was added dropwise, and the mixture was stirred overnight while gradually returning to room temperature. The reaction mixture was slowly poured into 200 ml of distilled water and extracted three times with 250 ml of dichloromethane. The resulting organic phase was washed with 120 ml of saturated brine and dried over anhydrous sodium sulfate. The sodium sulfate was filtered, the solvent was removed by vacuum distillation, and the solution was purified using a silica gel column (petroleum ether / ethyl acetate = 10 / 1) to obtain 12.00 g of yellow oil of 1,2-bis(1-indenylmethyl)-4,5-dimethylbenzene (yield 67%).

[0117] (1-3) Synthesis of meso-4,5-dimethyl-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride In a 200 ml flask, 1.99 g (5.49 mmol) of 1,2-bis(1-indenylmethyl)-4,5-dimethylbenzene and 60 ml of THF were added and cooled to -78°C. 7.20 ml (11.4 mmol) of n-butyllithium / n-hexane solution (1.58 M) was added dropwise, and the mixture was stirred for 3 hours at room temperature. A separately prepared solution of 1.54 g (6.61 mmol) of zirconium tetrachloride / 10 ml of n-hexane / 40 ml of THF was added at 0°C, and the mixture was stirred overnight while gradually returning to room temperature. A yellow powder was obtained by removing the solvent from the reaction mixture under reduced pressure. 35 ml of toluene was added to this powder at room temperature and stirred for 30 minutes. Insoluble matter was removed by filtration, and the solvent was removed from the resulting filtrate under reduced pressure to obtain another yellow powder. The resulting yellow powder was recrystallized in a mixed solvent of dichloromethane / n-hexane to obtain 0.284 g (10% yield) of meso-4,5-dimethyl-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (metallocene compound A) yellow powder. The toluene solubility of metallocene compound A was 40.3 μmol / ml.

[0118] 1 H-NMR value (CDCl3): δ2.35(s,6H),δ3.99(d,2H),δ4.13(d,2H),δ5.97(d,2H),δ6.01( d,2H), δ7.12(dd,2H), δ7.19(s,2H), δ7.31(dd,2H), δ7.42(d,2H), δ7.64(d,2H). <Metallocene compound A (meso compound)>

[0119] [ka]

[0120] (2) Metallocene compound B: Synthesis of racemic-4,5-dimethyl-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride The toluene-insoluble portion produced in the synthesis of metallocene compound A (1-3) was extracted with 30 ml of dichloromethane, and the extract was recrystallized to obtain 0.631 g (22% yield) of racemic-4,5-dimethyl-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (metallocene compound B) as a yellow powder. The toluene solubility of metallocene compound B was 8.57 μmol / ml. 1 H-NMR value (CDCl3): δ2.36(s,6H),δ4.15(d,2H),δ4.28(d,2H),δ5.69(s,br,2H),δ6 .23(s,br,2H),δ7.15(t,2H),δ7.25(s,br,4H),δ7.43(s,br,2H),δ7.58(d,2H). <Metallocene compound B (racemate)>

[0121] [ka]

[0122] (3) Synthesis of metallocene compound C: racemic-4,5-dichloro-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (3-1) Synthesis of 1,2-bis(hydroxymethyl)-4,5-dichlorobenzene In a 500 ml flask, 10.0 g (46.1 mmol) of 4,5-dichlorophthalic anhydride and 250 ml of THF were added and cooled to 0°C. 2.62 g (69.1 mmol) of lithium aluminum hydride was added, and the mixture was stirred at 25°C for 16 hours. The reaction mixture was quenched with 11 ml of distilled water and 3 ml of 15% sodium hydroxide aqueous solution, and the insoluble matter was removed by filtration. By distillation of the solvent from the filtrate, 8.70 g (yield 91.2%) of the crude product of 1,2-bis(hydroxymethyl)-4,5-dichlorobenzene was obtained.

[0123] (3-2) Synthesis of 1,2-bis(chloromethyl)-4,5-dichlorobenzene In a 500 ml flask, 6.00 g (29.0 mmol) of crude 1,2-bis(hydroxymethyl)-4,5-dichlorobenzene, 150 ml of dichloromethane, 11.0 g (57.7 mmol) of p-toluenesulfonyl chloride, 8.80 g (87.0 mmol) of triethylamine, and 354 mg (2.90 mmol) of dimethylaminopyridine were added, and the mixture was stirred at 25°C for 12 hours. 150 ml of distilled water was added, and extraction was performed three times with 150 ml of dichloromethane. The resulting organic phase was washed with 150 ml of saturated brine and dried over anhydrous sodium sulfate. Sodium sulfate was filtered off, and the solvent was removed by vacuum distillation. The mixture was purified by silica gel column chromatography to obtain 5.20 g (yield 73.5%) of 1,2-bis(chloromethyl)-4,5-dichlorobenzene.

[0124] (3-3) Synthesis of 1,2-bis(1-indenylmethyl)-4,5-dichlorobenzene In a 300 ml flask, 6.43 g (55.3 mmol) of indene and 150 ml of THF were added and cooled to -78°C. 22.66 ml (51.7 mmol) of n-butyllithium / n-hexane solution (2.50 M) was added dropwise, and the mixture was stirred for 2 hours at room temperature. The mixture was cooled again to -78°C, and 4.50 g (18.5 mmol) of 1,2-bis(chloromethyl)-4,5-dichlorobenzene / 20 ml of THF solution was added. The mixture was stirred for 16 hours at room temperature. The reaction mixture was slowly poured into 150 ml of distilled water and extracted three times with 150 ml of dichloromethane. The resulting organic phase was washed with 150 ml of saturated brine and dried over anhydrous sodium sulfate. Sodium sulfate was filtered, the solvent was removed by vacuum distillation, and the solution was purified using a silica gel column (petroleum ether) to obtain 3.80 g of 1,2-bis(1-indenylmethyl)-4,5-dichlorobenzene (yield 51.1%).

[0125] (3-4) Synthesis of racemic-4,5-dichloro-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride In a 200 ml flask, 1.21 g (3.00 mmol) of 1,2-bis(1-indenylmethyl)-4,5-dichlorobenzene and 50 ml of THF were added and cooled to -78°C. 3.95 ml (6.24 mmol) of n-butyllithium / n-hexane solution (1.58 M) was added dropwise, and the mixture was stirred at -78°C for 30 minutes, followed by stirring at room temperature for 1 hour. A separately prepared solution of 0.839 g (3.60 mmol) of zirconium tetrachloride / 5 ml of n-hexane / 20 ml of THF was added at 0°C, and the mixture was stirred at room temperature for 4 hours. The solvent was removed from the reaction mixture under reduced pressure to obtain a yellow powder. 60 ml of toluene was added to this powder at room temperature, and the insoluble matter was removed by filtration. The solvent was removed from the resulting filtrate under reduced pressure to obtain another yellow powder. The resulting yellow powder was recrystallized in a dichloromethane / diethyl ether mixed solvent to obtain 0.106 g (6% yield) of racemic-4,5-dichloro-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (metallocene compound C) yellow powder. The toluene solubility of metallocene compound C was 4.35 μmol / ml.

[0126] 1 H-NMR value (CDCl3): δ4.19(d,2H),δ4.32(d,2H),δ5.74(s,br,2H),δ6.28(s,br,2 H), δ7.19(t,2H), δ7.32(t,2H), δ7.47(s,br,2H), δ7.60(s,2H), δ7.62(d,2H). <Metallocene compound C (racemate)>

[0127] [ka]

[0128] (4) Synthesis of metallocene compound D: meso-4,5-dichloro-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride In the synthesis of metallocene compound C (3-4), a yellow powder was obtained by removing the solvent under reduced pressure from the mother liquor produced by recrystallization of a dichloromethane / diethyl ether mixed solvent. The obtained yellow powder was recrystallized with diethyl ether to obtain 0.079 g (yield 5%) of meso-4,5-dichloro-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (metallocene compound D) yellow powder. The toluene solubility of metallocene compound D was 6.76 μmol / ml. 1 H-NMR value (CDCl3): δ4.04(d,2H), δ4.16(d,2H), δ5.98(d,2H), δ6.07(d,2H) ,δ7.15(t,2H),δ7.33(t,2H),δ7.40(d,2H),δ7.56(s,2H),δ7.66(d,2H). <Metallocene compound D (meso compound)>

[0129] [ka]

[0130] (5) Metallocene compound E: Synthesis of racemic-4,5-dimethoxy-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (5-1) Synthesis of 1,2-bis(chloromethyl)-4,5-dimethoxybenzene In a 500 ml flask, 41.45 g (300.0 mol) of 1,2-dimethoxybenzene and 250 ml of dioxane were added and cooled to 0°C. 40.0 ml (403 mmol) of concentrated hydrochloric acid and 67.0 ml (900 mmol) of 37% formalin were added, and hydrogen chloride was blown in for 30 minutes. The reaction mixture was then heated to 40°C and stirred for 2 hours. The reaction mixture was concentrated by vacuum distillation, 200 ml of distilled water was added, and the mixture was extracted three times with 200 ml of dichloromethane. The resulting organic phase was washed with 200 ml of distilled water and dried over anhydrous sodium sulfate. The sodium sulfate was filtered off, and the solvent was removed by vacuum distillation to obtain 60.0 g (85.1% yield) of crude 1,2-bis(chloromethyl)-4,5-dimethoxybenzene.

[0131] (5-2) Synthesis of 1,2-bis(1-indenylmethyl)-4,5-dimethoxybenzene In a 500 ml flask, 14.82 g (127.6 mmol) of indene and 200 ml of THF were added and cooled to -78°C. 47.64 ml (119.1 mmol) of n-butyllithium / n-hexane solution (2.50 M) was added dropwise, and the mixture was stirred at 25°C for 2 hours. The mixture was cooled again to -78°C, and 10.0 g (42.5 mmol) of 1,2-bis(chloromethyl)-4,5-dimethoxybenzene / 50 ml of THF solution was added, and the mixture was stirred at 25°C for 16 hours. The reaction mixture was slowly poured into 300 ml of distilled water, and the mixture was extracted three times with 350 ml of dichloromethane. The resulting organic phase was washed with 300 ml of saturated brine and dried over anhydrous sodium sulfate. Sodium sulfate was filtered, the solvent was removed by vacuum distillation, and the solution was purified using a silica gel column (petroleum ether / ethyl acetate = 10 / 1) to obtain 9.20 g of 1,2-bis(1-indenylmethyl)-4,5-dimethoxybenzene (yield 54.8%).

[0132] (5-3) Synthesis of racemic-4,5-dimethoxy-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride 0.986 g (2.50 mmol) of 1,2-bis(1-indenylmethyl)-4,5-dimethoxybenzene and 50 ml of diethyl ether were added to a 100 ml flask and cooled to 0°C. 3.30 ml (5.21 mmol) of n-butyllithium / n-hexane solution (1.58 M) was added dropwise, and the mixture was stirred at room temperature for 4 hours. 0.699 g (3.00 mmol) of zirconium tetrachloride was added at 0°C, and the mixture was stirred at room temperature for 16 hours. Insoluble matter was collected from the reaction mixture by filtration, and the solvent was removed by vacuum distillation to obtain a yellow powder. 30 ml of toluene was added to this powder at room temperature, and the insoluble matter was removed by filtration. The solvent was removed from the resulting filtrate by vacuum distillation to obtain another yellow powder. The resulting yellow powder was washed three times with 10 ml of hexane and recrystallized in a dichloromethane / diethyl ether mixed solvent to obtain 0.230 g (17% yield) of racemic-4,5-dimethoxy-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (metallocene compound E) yellow powder. The toluene solubility of metallocene compound E was 10.8 μmol / ml.

[0133] 1 H-NMR value (CDCl3): δ3.96(s,6H),δ4.16(d,br,2H),δ4.27(d,2H),δ5.72(s,br,2H),δ6.21(s, br,2H), δ7.01(s,br,2H), δ7.15(t,2H), δ7.24(s,br,2H), δ7.37(s,br,2H), δ7.59(d,2H). <Metallocene compound E (racemic mixture)>

[0134] [ka]

[0135] (6) Synthesis of metallocene compound F: meso-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride For the metallocene compound F, meso-1 was synthesized according to the procedure of Complex 1 described in the Experimental Section of Macromolecules 1995, 28, 4801 - 4805, and this was used as the metallocene compound F. The toluene solubility of the metallocene compound F was 1.56 μmol / ml. <Metallocene Compound F (meso form)>

[0136] [Chemical formula]

[0137] (7) Metallocene Compound G: Synthesis of meso-1,2-phenylenebis(methylene(4,7-dimethyl-1-indenyl))zirconium dichloride The metallocene compound G was synthesized according to the synthesis procedure of [o-xylene-α,α'-bis-(η5-(4,7-dimethyl)-1-indenyl)]-zirconium dichloride described in Example 2 of JP-A-9-286812. The toluene solubility of the metallocene compound G was 3.76 μmol / ml. <Metallocene Compound G (meso form)>

[0138] [Chemical formula]

[0139] (8) Metallocene Compound H: Synthesis of meso-4,5-dimethyl-1,2-phenylenebis(methylene(1-indenyl))zirconium dimethyl 1.01 g (2.79 mmol) of 1,2-bis(1-indenylmethyl)-4,5-dimethylbenzene and 60 ml of THF were added to a 100 ml flask and cooled to -78 °C. 3.93 ml (6.13 mmol) of an n-butyllithium / n-hexane solution (1.56 M) was added dropwise thereto, and the mixture was returned to room temperature and stirred for 2 hours (Reaction Solution 1). 0.645 g (2.77 mmol) of zirconium tetrachloride was added to a separately prepared 300 ml flask and cooled to -78 °C. 90 ml of THF was gradually added thereto, and subsequently, 5.54 ml (6.09 mmol) of a methyllithium / diethyl ether solution (1.1 M) was added dropwise over 5 minutes, and the mixture was stirred at -78 °C for 30 minutes. The previously prepared Reaction Solution 1 was added dropwise thereto at -78 °C over 20 minutes, and the mixture was stirred at room temperature for 4 hours. The solvent was distilled off under reduced pressure from the reaction solution to obtain a brown powder. 100 ml of toluene was added to this powder at room temperature and stirred for 30 minutes. The insoluble matter was removed by filtration, and the solvent was distilled off under reduced pressure from the obtained filtrate to concentrate it, whereby a brown powder was precipitated. The precipitated brown powder was collected by filtration, washed twice with 3 ml of hexane, and dried under reduced pressure to obtain 0.726 g (yield 55%) of a white powder of meso-4,5-dimethyl-1,2-phenylenebis(methylene(1-indenyl))zirconium dimethyl (Metallocene Compound H). The toluene solubility of Metallocene Compound H was 69.3 μmol / ml.

[0140] 1 H-NMR value (CDCl3): δ -2.92 (s, 3H), -0.37 (s, 3H), 2.30 (s, 6H), δ 3.95 (q, 4H), δ 5.10 (d, 2H), δ 5.98 (d, 2H), δ 7.06 (dt, 2H), δ 7.10 (s, 2H), δ 7.23 (dt, 2H), δ 7.35 (dd, 2H), δ 7.57 (d, 2H). <Metallocene Compound H (meso form)>

[0141]

Chemical formula

[0142] (9) Metallocene compound I: Synthesis of meso-3,4,5,6-tetrachloro-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (9-1) Synthesis of 1,2-bis(hydroxymethyl)-3,4,5,6-tetrachlorobenzene In a 100 ml flask, 1.00 g (3.50 mmol) of tetrachlorophthalic anhydride and 15 ml of THF were added. 22.74 ml (22.74 mol) of 1.0 M diisobutylaluminum hydride / hexane solution was gradually added at room temperature, and the mixture was stirred for 1.5 hours. Subsequently, 25 ml of 10% hydrochloric acid at 0°C was added, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was filtered through Celite, and the filtrate was extracted three times with 50 ml of ethyl acetate. The organic phase was washed with 50 ml of saturated brine and dried over anhydrous sodium sulfate. The sodium sulfate was filtered off, and the solvent was removed under reduced pressure to obtain 0.80 g (83% yield) of 1,2-bis(hydroxymethyl)-3,4,5,6-tetrachlorobenzene as a white powder.

[0143] (9-2) Synthesis of 1,2-bis(chloromethyl)-3,4,5,6-tetrachlorobenzene 0.30 g (1.09 mmol) of 1,2-bis(hydroxymethyl)-3,4,5,6-tetrachlorobenzene and 10 ml of dichloromethane were added to a 50 ml flask. 518.17 mg (2.72 mmol) of p-toluenesulfonyl chloride, 13.28 mg (108.7 μmol) of 4-dimethylaminopyridine, and 275.03 mg (2.72 mmol) of triethylamine were added at room temperature, and the mixture was stirred at 25°C for 12 hours. The reaction mixture was added to 50 ml of distilled water and extracted three times with 50 ml of dichloromethane. The organic phase was washed with 50 ml of saturated brine and dried over anhydrous sodium sulfate. The sodium sulfate was filtered off, the solvent was removed under reduced pressure, and the mixture was purified by silica gel column (petroleum ether) to obtain 0.19 g (56% yield) of 1,2-bis(hydroxymethyl)-3,4,5,6-tetrachlorobenzene as a white powder.

[0144] (9-3) Synthesis of 1,2-bis(1-indenylmethyl)-3,4,5,6-tetrachlorobenzene In a 500 ml flask, 6.54 g (56.3 mmol) of indene and 160 ml of THF were added and cooled to -78°C. 21.48 ml (53.7 mmol) of n-butyllithium / n-hexane solution (2.50 M) was added dropwise, and the mixture was stirred at room temperature for 3 hours. The mixture was cooled again to -78°C, and 8.00 g (25.6 mmol) of 1,2-bis(chloromethyl)-3,4,5,6-tetrachlorobenzene / THF solution was added in 20 ml of THF solution. The mixture was stirred at room temperature for 16 hours. The reaction mixture was slowly poured into 200 ml of distilled water and extracted three times with 100 ml of dichloromethane. The resulting organic phase was washed with 250 ml of saturated brine and dried over anhydrous sodium sulfate. Sodium sulfate was filtered, the solvent was removed by vacuum distillation, and the solution was purified using a silica gel column (petroleum ether / ethyl acetate = 10 / 1) to obtain 16.2 g of 1,2-bis(1-indenylmethyl)-3,4,5,6-tetrachlorobenzene (yield 67.1%).

[0145] (9-4) Meso-3,4,5,6-tetrachloro-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride In a 200 ml flask, 1.983 g (4.2 mmol) of 1,2-bis(1-indenylmethyl)-3,4,5,6-tetrachlorobenzene and 100 ml of THF were added and cooled to -78°C. 5.5 ml (8.7 mmol) of n-butyllithium / n-hexane solution (1.59 M) was added dropwise, and the mixture was stirred at -78°C for 30 minutes. Then, 1.174 g (5.04 mmol) of zirconium tetrachloride was added, and the mixture was stirred at -78°C for 2 hours, followed by stirring at room temperature for another 2 hours. The solvent was removed from the reaction mixture under reduced pressure to obtain a black, viscous substance. This substance was washed with 45 ml of diethyl ether, and the remaining solid was extracted with 35 ml of toluene. By removing toluene from the extract under reduced pressure, 0.590 g (22% yield) of meso-3,4,5,6-tetrachloro-1,2-phenylenebis(methylene(1-indenyl))zirconium dichloride (metallocene compound I) yellow powder was obtained. The toluene solubility of metallocene compound I was 8.36 μmol / ml.

[0146] 1H-NMR value (CDCl3): δ4.12(d,2H), δ4.21(dd,2H), δ4.67(d,2H), δ4.75(dd,2H), δ5.92 (t,2H), δ6.11(t,2H), δ7.16(dt,2H), δ7.36(dt,2H), δ7.42(dd,2H), δ7.69(t,2H). <Metallocene compound I (meso compound)>

[0147] [ka]

[0148] 3. Production of olefin polymers [Example 1] (1) Preparation of solid catalyst 1 Under a nitrogen atmosphere, 3g of silica (component (C)) calcined at 400°C for 7 hours was placed in a 200ml two-necked flask and dried under reduced pressure using a vacuum pump while heating in a 150°C oil bath for 1 hour. 39 mg of metallocene compound A (component (A)) was placed in a separately prepared 100 ml two-necked flask under a nitrogen atmosphere and dissolved in 15.0 ml of anhydrous toluene. No insoluble matter was found. At room temperature, 8.3 ml of 20% methylaluminoxane (component (B)) / toluene solution manufactured by Albemarle was added to the toluene solution of metallocene compound A (component (A)) and stirred for 1 hour (Al / Zr molar ratio = 320). Vacuum-dried silica (component (C)) was mixed with 30.0 ml of toluene and heated and stirred in an oil bath at 40°C. The entire volume of the toluene solution of the reaction product of metallocene compound A (component (A)) and methyl aluminoxane (component (B)) was then added. After stirring at 40°C for 1 hour, the mixture was allowed to stand, the supernatant was removed, and the toluene solvent was removed under reduced pressure while the mixture remained heated at 40°C to obtain solid catalyst 1 (catalyst for olefin polymerization).

[0149] (2) Production of ethylene-1-hexene copolymer In a 2.0-liter stainless steel autoclave equipped with stirring and temperature control devices, 1.26 mmol of triisobutylaluminum (TiBA), 7.5 ml of 1-hexene, and 1000 ml of thoroughly dehydrated and deoxygenated isobutane were introduced as scavengers, and the temperature was raised to 70°C while stirring. Once the temperature stabilized, 50 ml (2.2 mmol) of hydrogen and ethylene were introduced until the partial pressure reached 1.0 MPa. 5.0 ml of hexane slurry of 20.0 mg of the above solid catalyst 1 was injected under pressure with argon gas, and polymerization was continued for 60 minutes while maintaining an ethylene partial pressure of 1.0 MPa and a temperature of 70°C. After that, the pressure inside the autoclave was released, the ethylene-1-hexene copolymer was recovered, and dried in a vacuum dryer at 80°C for 1 hour. During the polymerization reaction, hydrogen was supplied at an amount of 0.8 mol% relative to ethylene in proportion to the ethylene consumption rate. The molar ratio of hydrogen to ethylene in the gas phase of the autoclave was 0.025 mol% before polymerization began, compared to 0.023 mol% at the end of polymerization. As a result, 38.5 g of ethylene·1-hexene copolymer 1 was produced. The resulting copolymer had a molecular weight (MFR) of 0.49 g / 10 min and a density of 0.9510 g / cm³. 3 The polymerization conditions are summarized in Table 2, and the polymerization results are summarized in Table 3. In Table 2, methyl aluminoxane (component (B)) is denoted as "MAO," and ethylene partial pressure is denoted as "C2 partial pressure."

[0150] [Example 2] (1) Production of ethylene-1-hexene copolymer Ethylene-1-hexene copolymer 2 was produced in the same manner as in Example 1, except that 300 ml (13.4 mmol) of hydrogen was introduced before the catalyst was introduced, and the hydrogen supply during the polymerization reaction was 4.0 mol% relative to ethylene. As a result, 33.9 g of ethylene-1-hexene copolymer 2 was produced. The resulting copolymer had a molecular weight (MFR) of 7.23 g / 10 min and a density of 0.9609 g / cm³. 3 The polymerization conditions are summarized in Table 2, and the polymerization results are summarized in Table 3.

[0151] [Example 3] (1) Preparation of solid catalyst 2 A solid catalyst 2 was prepared in the same manner as in Example 1, except that 39 mg of metallocene compound B (component (A)) was used instead of 39 mg of metallocene compound A (component (A)). There was no insoluble matter. (2) Production of ethylene-1-hexene copolymer 3 Ethylene-1-hexene copolymer 3 was produced in the same manner as in Example 1, except that the above solid catalyst 2 was used instead of solid catalyst 1 and the hydrogen supply during the polymerization reaction was set to 0.04 mol% with respect to ethylene. As a result, 35.8 g of ethylene-1-hexene copolymer 3 was produced. The MFR of the obtained copolymer was 0.17 g / 10 min, and the density was 0.9454 g / cm 3 It was. The polymerization conditions are summarized in Table 2, and the polymerization results are summarized in Table 3.

[0152] [Example 4] (1) Production of ethylene-1-hexene copolymer Ethylene-1-hexene copolymer 4 was produced in the same manner as in Example 3, except that the hydrogen introduced before introducing the catalyst was set to 150 ml (6.70 mmol) and the hydrogen supply during the polymerization reaction was set to 6.0 mol% with respect to ethylene. As a result, 54.0 g of ethylene-1-hexene copolymer 4 was produced. The MFR of the obtained copolymer was 40.06 g / 10 min, and the density was 0.9668 g / cm 3 It was. The polymerization conditions are summarized in Table 2, and the polymerization results are summarized in Table 3.

[0153] [Example 5] (1) Preparation of solid catalyst 3 A solid catalyst 3 was prepared in the same manner as in Example 1, except that 42 mg of metallocene compound C (component (A)) was used instead of 39 mg of metallocene compound A (component (A)) and 20.0 mL of toluene was used instead of 15 mL of toluene. There was no insoluble matter. (2) Production of ethylene-1-hexene copolymer Ethylene-1-hexene copolymer 5 was produced in the same manner as in Example 1, except that solid catalyst 3 was used instead of solid catalyst 1, 300 ml (13.4 mmol) of hydrogen was introduced before introducing the catalyst, and the hydrogen supply during the polymerization reaction was 0.03 mol% relative to ethylene. As a result, 52.7 g of ethylene-1-hexene copolymer 5 was produced. The resulting copolymer had an MFR of 67.90 g / 10 min and a density of 0.9608 g / cm³. 3 The polymerization conditions are summarized in Table 2, and the polymerization results are summarized in Table 3.

[0154] [Example 6] (1) Preparation of solid catalyst 4 Solid catalyst 4 was prepared in the same manner as in Example 1, except that 42 mg of metallocene compound D (component (A)) was used instead of 39 mg of metallocene compound A (component (A)). No insoluble matter was found. (2) Production of ethylene-1-hexene copolymer Ethylene-1-hexene copolymer 6 was produced in the same manner as in Example 1, except that solid catalyst 4 was used instead of solid catalyst 1, and the hydrogen supply during the polymerization reaction was set to 8.0 mol% relative to ethylene. As a result, 61.1 g of ethylene·1-hexene copolymer 6 was produced. The resulting copolymer had an MFR of 0.34 g / 10 min and a density of 0.9483 g / cm³. 3 The polymerization conditions are summarized in Table 2, and the polymerization results are summarized in Table 3.

[0155] [Example 7] (1) Preparation of solid catalyst 5 Solid catalyst 5 was prepared in the same manner as in Example 1, except that 42 mg of metallocene compound E (component (A)) was used instead of 39 mg of metallocene compound A (component (A)). No insoluble matter was found. (2) Production of ethylene-1-hexene copolymer Ethylene-1-hexene copolymer 7 was produced in the same manner as in Example 1, except that solid catalyst 5 was used instead of solid catalyst 1, 300 ml (13.4 mmol) of hydrogen was introduced before introducing the catalyst, and the hydrogen supply during the polymerization reaction was 8.0 mol% relative to ethylene. As a result, 28.0 g of ethylene-1-hexene copolymer 7 was produced. The resulting copolymer had a molecular weight (MFR) of 41.20 g / 10 min and a density of 0.9659 g / cm³. 3 The polymerization conditions are summarized in Table 2, and the polymerization results are summarized in Table 3.

[0156] [Example 8] (1) Preparation of solid catalyst 8 Solid catalyst 8 was prepared in the same manner as in Example 1, except that 36 mg of metallocene compound H (component (A)) was used instead of 39 mg of metallocene compound A (component (A)). No insoluble matter was found. (2) Production of ethylene-1-hexene copolymer Ethylene-1-hexene copolymer 9 was produced in the same manner as in Example 1, except that solid catalyst 8 was used instead of solid catalyst 1. As a result, 57.8 g of ethylene-1-hexene copolymer 9 was produced. The resulting copolymer had a molecular weight (MFR) of 0.24 g / 10 min and a density of 0.9483 g / cm³. 3 The polymerization conditions are summarized in Table 2, and the polymerization results are summarized in Table 3.

[0157] [Example 9] (1) Production of ethylene-1-hexene copolymer Ethylene-1-hexene copolymer 10 was produced in the same manner as in Example 8, except that 500 ml (22.3 mmol) of hydrogen was introduced before the catalyst was introduced, and the hydrogen supply during the polymerization reaction was 6.0 mol% relative to ethylene. As a result, 53.7 g of ethylene-1-hexene copolymer 10 was produced. The resulting copolymer had an MFR of 14.96 g / 10 min and a density of 0.9632 g / cm³. 3 The polymerization conditions are summarized in Table 2, and the polymerization results are summarized in Table 3.

[0158] [Example 10] (1) Preparation of solid catalyst 9 Solid catalyst 9 was prepared in the same manner as in Example 1, except that 47 mg of metallocene compound I (component (A)) was used instead of 39 mg of metallocene compound A (component (A)). No insoluble matter was found. (2) Production of ethylene-1-hexene copolymer Ethylene-1-hexene copolymer 11 was produced in the same manner as in Example 1, except that the above-mentioned solid catalyst 9 was used instead of solid catalyst 1, and the hydrogen supply during the polymerization reaction was set to 0.06 mol% relative to ethylene. As a result, 25.7 g of ethylene-1-hexene copolymer 11 was produced. The resulting copolymer had a molecular weight (MFR) of 0.89 g / 10 min and a density of 0.9554 g / cm³. 3 The polymerization conditions are summarized in Table 2, and the polymerization results are summarized in Table 3.

[0159] [Example 11] (1) Production of ethylene-1-hexene copolymer Ethylene-1-hexene copolymer 12 was produced in the same manner as in Example 10, except that 300 ml (13.4 mmol) of hydrogen was introduced before the catalyst was introduced, and the hydrogen supply during the polymerization reaction was 8.0 mol% relative to ethylene. As a result, 19.3 g of ethylene-1-hexene copolymer 12 was produced. The resulting copolymer had a molecular weight (MFR) of 29.15 g / 10 min and a density of 0.9691 g / cm³. 3 The polymerization conditions are summarized in Table 2, and the polymerization results are summarized in Table 3.

[0160] [Comparative Example 1] (1) Preparation of solid catalyst 6 When 37 mg of metallocene compound F was placed in a 100 ml two-necked flask under a nitrogen atmosphere and 15.0 ml of anhydrous toluene was added, some solid matter remained undissolved (69% by weight), so catalytic activation was not performed.

[0161] [Comparative Example 2] (1) Preparation of solid catalyst 7 Solid catalyst 7 was prepared in the same manner as in Example 1, except that 41 mg of metallocene compound G was used instead of 39 mg of metallocene compound A (component (A)), and 25.0 mL of toluene was used instead of 15 mL of toluene. No insoluble matter was found. (2) Production of ethylene-1-hexene copolymer Ethylene-1-hexene copolymer 8 was produced in the same manner as in Example 1, except that 100 mg of the above-mentioned solid catalyst 7 was used instead of 20 mg of solid catalyst 1, 60 ml (2.68 mmol) of hydrogen was introduced before the catalyst was introduced, and the hydrogen supply during the polymerization reaction was 4.0 mol% relative to ethylene. As a result, 29.2 g of ethylene-1-hexene copolymer 8 was produced. The resulting copolymer had a molecular weight (MFR) of 0.19 g / 10 min and a density of 0.9537 g / cm³. 3 The polymerization conditions are summarized in Table 2, and the polymerization results are summarized in Table 3.

[0162] [Table 2]

[0163] [Table 3]

[0164] 4. Discussion In Comparative Example 1, a metallocene compound F, which had no substituents on either the orthoxylene skeleton (the crosslinking portion) or the indenyl skeleton (the ligand), was used as the catalytic active ingredient. However, the solubility of metallocene compound F in toluene was low at 1.56 μmol / ml, and although an attempt was made to prepare a complex solution a with the same molar concentration (5.0 mmol / L) as in Example 1, there were undissolved particles, so catalysis was not performed. In Comparative Example 2, metallocene compound G, which has the same molecular skeleton as the metallocene compound in Comparative Example 1, and does not have substituents on the orthoxylene skeleton which is the crosslinking portion, but has substituents on the indenyl skeleton which is the ligand (i.e., it has a 4,7-dimethyl-1-indenyl structure), was used as the catalytic active component. The solubility of metallocene compound G in toluene was 3.76 μmol / ml, which was greater than that of metallocene compound F in Comparative Example 1. Using this metallocene compound G, a completely dissolved complex solution a with a concentration of 3.0 mmol / L could be prepared, and catalysis was achieved. However, the solid catalyst 7 produced using the complex solution a of metallocene compound G had an activity of 292 g-PE / g-Cat / hr per solid catalyst and an activity of 17 g-PE / μmol-Zr / hr per complex, and sufficient polymerization activity was not obtained. It is thought that the metallocene compound G in Comparative Example 2 did not obtain sufficient polymerization activity because the substituent on the indenyl skeleton which is the ligand had an effect of shielding the polymerization field.

[0165] On the other hand, in Example 1, metallocene compound A, which has the same molecular skeleton as the metallocene compound of Comparative Example 1 and has substituents on the orthoxylene skeleton which is the crosslinking portion (i.e., it has a 4,5-dimethyl-1,2-phenylene structure), but does not have substituents on the indenyl skeleton which is the ligand, was used as the catalytic active component. The solubility of metallocene compound A in toluene was 40.3 μmol / ml, which was greater than that of metallocene compound F of Comparative Example 1, and even more significantly greater than that of metallocene compound G of Comparative Example 2, which has substituents on the indenyl skeleton which is the ligand. Using this metallocene compound A, a completely dissolved complex solution a with a concentration of 5.0 mmol / L could be prepared and catalyzed. The solid catalyst 1 produced using the complex solution a of metallocene compound A had an activity of 1925 g-PE / g-Cat / hr per solid catalyst and an activity of 114 g-PE / μmol-Zr / hr per complex, indicating high polymerization activity. The metallocene compound A of Example 1 was found to have excellent solvent solubility and to possess sufficient capabilities as a catalyst component.

[0166] In Example 2, when the solid catalyst 1 from Example 1 was used and the amount of hydrogen supplied during the polymerization process was changed, high polymerization activity was obtained, similar to Example 1. In Examples 3 and 4, metallocene compound B (racemic mixture), an isomer of metallocene compound A (meso compound) from Example 1, was used, and the amount of hydrogen supplied during the polymerization process was changed. As with Example 1, high polymerization activity was obtained. Based on the results from Examples 1 and 2 and Examples 3 and 4, it is considered that the metallocene compounds of the present invention can be found to have high polymerization activity whether they are meso or racemic. In Example 5, instead of metallocene compound B (racemate) used in Examples 3 and 4, metallocene compound C (racemate) in which a chlorine atom was substituted at the same substitution position as metallocene compound B was used, and the amount of hydrogen supplied during the polymerization process was changed. As with Examples 3 and 4, high polymerization activity was obtained. In Example 6, instead of metallocene compound A (meso compound) from Example 1, metallocene compound D (meso compound) in which a chlorine atom was substituted at the same substitution position as metallocene compound A was used, and the amount of hydrogen supplied during the polymerization process was changed. As with Example 1, high polymerization activity was obtained. In Example 7, instead of metallocene compound B (racemate) from Examples 3 and 4, metallocene compound E (racemate), in which a methoxy group is substituted at the same substitution position as metallocene compound B, was used, and the amount of hydrogen supplied during the polymerization process was changed. As with Example 2, high polymerization activity was obtained.

[0167] In Example 8, instead of metallocene compound A (meso form) from Example 1, metallocene compound H (meso form), which is a dimethyl form in which the two chlorine atoms bonded to Zr of metallocene compound A are replaced with methyl atoms, was used, and high polymerization activity was obtained, similar to Example 1. In Example 9, when the solid catalyst 8 from Example 8 was used and the amount of hydrogen supplied during the polymerization process was changed, high polymerization activity was obtained, similar to Example 8. In Example 10, instead of metallocene compound A (meso compound) from Example 1, metallocene compound I (meso compound), in which two additional chlorine atoms were substituted on the orthoxylene at the crosslinking portion of metallocene compound D, was used, and the amount of hydrogen supplied during the polymerization process was changed. As with Example 1, high polymerization activity was obtained. In Example 11, when the solid catalyst 9 from Example 10 was used and the amount of hydrogen supplied during the polymerization process was changed, a much higher polymerization activity was obtained than in Comparative Example 2. [Industrial applicability]

[0168] The metallocene compounds of the present invention exhibit excellent solvent solubility and possess sufficient catalytic activity, allowing for the preparation of high-concentration complex solutions and yielding polymerization catalysts with high polymerization activity. Furthermore, their excellent solvent solubility prevents instability or failure of catalytic performance due to undissolved residue during catalyst production. Moreover, the metallocene compounds of the present invention are easily soluble in solvents during synthesis and purification, enabling efficient production. Therefore, the metallocene compounds and catalysts of the present invention can be used to polymerize or copolymerize olefin monomers, and in particular, can efficiently produce ethylene polymers.

Claims

1. A metallocene compound represented by the following general formula (1). 【Chemistry 1】 [In general formula (1), M represents one of the transition metals Ti, Zr, or Hf. X １ and X ２ Each of these independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom, a hydrocarbon group substituted with 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. R １ 、R ２ 、R ３ 、R ４ 、R ５ 、R ６ 、R ７ 、R ８ 、R ９ 、R １０ 、R １１ 、R １２ 、R １３ 、R １４ 、R １５ and R １６ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing an oxygen atom, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms containing 1 to 6 silicon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms. However, R １ , R ２ , R ３ and R ４ At least one of them represents an atom or group other than a hydrogen atom.

2. In the above general formula (1), R １ , R ２ , R ３ and R ４ The metallocene compound according to claim 1, wherein each is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, and at least one of them is an atom or group other than a hydrogen atom.

3. A catalyst for olefin polymerization comprising the following components (A) and (B). Component (A): Metallocene compound according to claim 1 Component (B): A compound that reacts with component (A) to produce a cationic metallocene compound.

4. A catalyst for olefin polymerization comprising the following components (A), (B), and (C). Component (A): Metallocene compound according to claim 1 Component (B): A compound that reacts with component (A) to produce a cationic metallocene compound. Component (C): Particulate carrier

5. The catalyst for olefin polymerization according to claim 3 or 4, wherein the component (B) is an aluminoxane.

6. The catalyst for olefin polymerization according to claim 4, wherein the component (C) is silica.

7. The catalyst for olefin polymerization according to claim 3 or 4, further comprising component (D) an organoaluminum compound.

8. A catalyst for olefin polymerization comprising contacting at least the following components (A) and (B). Component (A): Metallocene compound according to claim 1 Component (B): A compound that reacts with component (A) to produce a cationic metallocene compound.

9. A catalyst for olefin polymerization comprising contacting at least the following components (A), (B), and (C). Component (A): Metallocene compound according to claim 1 Component (B): A compound that reacts with component (A) to produce a cationic metallocene compound. Component (C): Particulate carrier

10. The catalyst for olefin polymerization according to claim 8 or 9, further comprising contact with component (D) an organoaluminum compound.

11. A method for producing an olefin polymerization catalyst, characterized by contacting the following components (A) and (B). Component (A): Metallocene compound according to claim 1 Component (B): A compound that reacts with component (A) to produce a cationic metallocene compound.

12. A method for producing an olefin polymerization catalyst, characterized by contacting the following components (A), (B), and (C). Component (A): Metallocene compound according to claim 1 Component (B): A compound that reacts with component (A) to produce a cationic metallocene compound. Component (C): Particulate carrier

13. A method for producing an olefin polymerization catalyst according to claim 12, comprising the following steps. Step 1: Mix component (A) with a hydrocarbon solvent to prepare complex solution a.

14. A method for producing an olefin polymerization catalyst according to claim 13, further comprising the following steps 2 and 3. Step 2: Mix the complex solution a obtained in Step 1 with component (B) to prepare a mixed solution b. Step 3: Mix the mixture b obtained in Step 2 with component (C) to prepare slurry c.

15. A method for producing an olefin polymerization catalyst according to claim 14, further comprising the following step 4. Step 4: Dry the slurry c obtained in Step 3.

16. The method for producing an olefin polymerization catalyst according to claim 13, wherein in step 1, the molar concentration of component (A) in the complex solution a is 2.5 mmol / L or more and 100 mmol / L or less.

17. The method for producing an olefin polymerization catalyst according to claim 13, wherein in step 1, the molar concentration of component (A) in the complex solution a is 3.0 mmol / L or more and 50 mmol / L or less.

18. The method for producing an olefin polymerization catalyst according to claim 12, wherein the amount of component (B) used is greater than 0.1 and less than or equal to 100,000 in molar ratio [component (B) / component (A)] with respect to component (A).

19. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin monomer in the presence of the olefin polymerization catalyst described in claim 3 or 4.

20. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin monomer in the presence of an olefin polymerization catalyst obtained from the production method described in claim 12.

21. A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin monomer in the presence of an olefin polymerization catalyst obtained from the production method described in claim 15.

22. A method for producing an olefin polymer according to claim 19, wherein the olefin monomer comprises at least ethylene.

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