JP2004217925A - Catalyst for polymerization of olefin and method for polymerization of olefin using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly active catalyst for polymerization of olefin that produces a polyolefin having high melt tension, excellent mechanical strength, reduced neck-in in T-die molding, and excellent in properties of particle. <P>SOLUTION: The catalyst for polymerization of olefin is obtained by prepolymerizing ethylene or ethylene/α-olefin by using a solid catalyst component which is obtained by contacting (A) a compound of a transition metal of group 4 of the periodic table wherein the compound has at least one ligand having a cyclopentadienyl skeleton, (B) an organic aluminumoxy compound and (C) a multi-functional organic halide, with a solid carrier to obtain 0.01-1000g of polymers per 1g of the solid catalyst component wherein the polymers have ≥600×10<SP>4</SP>of Z-average molecular weight measured by gel-permeation chromatography, and a die swell ratio of ≥1.4. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a solid catalyst for olefin polymerization and a method for polymerizing olefins using the catalyst, and more specifically, has a high melt tension, excellent mechanical strength, small neck-in in T-die molding, and excellent particle properties. The present invention relates to an olefin polymerization catalyst capable of producing an olefin polymer having a high polymerization activity and a method for polymerizing an olefin using the catalyst.

  Conventionally, as a catalyst for producing an olefin polymer, for example, an ethylene polymer or an ethylene / olefin copolymer, a Ziegler-type titanium-based catalyst comprising a titanium compound and an organoaluminum compound, or a vanadium compound and an organoaluminum compound is used. Vanadium-based catalysts are known.

  Further, as a catalyst capable of producing an ethylene-olefin copolymer with high polymerization activity, an olefin polymerization catalyst (metallocene catalyst) comprising a zirconium compound and an organic aluminum oxy compound (alumoxane) is known. A method for producing an ethylene / olefin copolymer using a catalyst is disclosed in, for example, JP-A-58-19309, JP-A-60-35005, JP-A-60-35006, and JP-A-60-35007. And Japanese Patent Application Laid-Open No. Sho 60-35008.

  Further, JP-A-60-260602 and JP-A-60-130604 disclose the polymerization of olefins using a catalyst formed from a transition metal compound and a mixed organoaluminum compound of an alumoxane and an organoaluminum compound. A way to do that has been proposed.

  However, in any of the ethylene polymer or the ethylene / olefin copolymer produced using the above-described catalyst, the melt tension and the melt viscoelasticity are insufficient, for example, the swing of a valve at the time of forming an inflation film, Alternatively, there is a limit to high-speed molding in a stable state without breaking. Further, even in hollow molding requiring similar characteristics, phenomena such as sagging or tearing are likely to occur. Furthermore, when a cast film is to be formed in T-die forming, there is a problem that a neck-in occurs in which the film end shrinks toward the center. When the neck-in occurs, the film width becomes smaller and the thickness of the film end becomes larger than that of the film center, so that the product yield is deteriorated.

  By the way, many methods have been proposed for improving the moldability by improving the melt tension and expansion ratio (die swell ratio) of the ethylene polymer. For example, a method using a Ziegler type titanium-based catalyst is disclosed in JP-A-56-90810 or JP-A-60-106806. Further, among the ethylene polymers produced using a Ziegler-type catalyst, the ethylene polymer obtained using a chromium-based catalyst has a relatively high melt tension, although the thermal stability is inferior. This is presumably because the chain ends of the ethylene polymer produced using the chromium-based catalyst tend to be unsaturated bonds. However, ethylene polymers, particularly low-density ethylene copolymers, obtained using titanium-based catalysts or chromium-based catalysts generally have problems such as a wide composition distribution and the formation of films and other molded articles having stickiness. Was.

  On the other hand, an ethylene polymer obtained using a metallocene catalyst has low melt tension, but excellent mechanical strength such as tensile strength, tear strength or impact strength, narrow composition distribution, and molded articles such as films are sticky. It is known that there are advantages such as little. A method for utilizing the advantages of the metallocene catalyst and improving the melt tension is described in, for example, JP-A-4-213306 (method of copolymerizing ethylene and an α-olefin such as 1-butene), and JP-T-1-50163. Publications (method of copolymerizing ethylene and 1,3-butadiene), and Japanese Patent Publication No. 4-506372 (method of copolymerizing ethylene and 1,4-hexadiene) have been proposed. However, in these methods, when a small amount of a comonomer branch or a crosslinked structure is introduced, the melting properties are not sufficiently improved. Also, when introduced in a large amount, there is a concern that the mechanical properties inherent to the polymer may be reduced or a gel may be generated.

  On the other hand, low-density polyethylene produced by a high-pressure radical polymerization method has a higher melt tension than an ethylene-based polymer produced using a Ziegler-type catalyst, and is used for applications such as films and hollow containers. However, the high-pressure method low-density polyethylene described above has a problem that it is inferior in mechanical strength such as tensile strength, tear strength or impact strength, and is also inferior in heat resistance and stress crack resistance.

  In order to solve this problem, a composition of a high-pressure low-density polyethylene having a high melt tension and an ethylene polymer having excellent mechanical strength obtained by using a metallocene catalyst is disclosed in, for example, WO 99/46325. Proposed. However, in order to prepare the composition, it is necessary to perform melt blending, and a significant increase in cost due to this blending is inevitable.

As described above, it has been difficult to efficiently and inexpensively obtain a resin having a high melt tension and excellent mechanical strength using a conventionally known technique such as a catalyst system or a resin blend. In other words, the emergence of an efficient technique for producing an ethylene polymer having both high melt tension and excellent mechanical strength is important for industrial production and its value is extremely high.
JP-A-58-19309 JP-A-60-35005 JP-A-60-35006 JP-A-60-35007 JP-A-60-35008 JP-A-60-260602 JP-A-60-130604 JP-A-56-90810 JP-A-60-106806 JP-A-4-213306 Japanese Patent Publication No. Hei 1-50163 Japanese Patent Publication No. 4-506372 WO99 / 46325

  The present invention has been made in view of the prior art as described above, and provides an olefin polymer having a high melt tension, excellent mechanical strength, a small neck-in in T-die molding, and excellent particle properties. It is an object of the present invention to provide an olefin polymerization catalyst that can be produced with high polymerization activity.

  The first olefin polymerization catalyst according to the present invention comprises: (A) a transition metal compound belonging to Group 4 of the Periodic Table containing at least one ligand having a cyclopentadienyl skeleton on a solid support; An ethylene or ethylene / a-olefin is brought into contact with a solid catalyst component carrying an oxy compound and the Z-average molecular weight by gel permeation chromatography is 6,000,000 or more, and the die swell ratio is 1.4 or more. It is characterized in that a certain polymer is prepolymerized in an amount of 0.01 to 1000 g per 1 g of the solid catalyst component.

  The second olefin polymerization catalyst according to the present invention comprises: (A) a transition metal compound belonging to Group 4 of the periodic table containing at least one ligand having a cyclopentadienyl skeleton, and (B) an organoaluminum. The solid catalyst component obtained by contacting the oxy compound with the polyfunctional organic halide (C) is contacted with ethylene or ethylene / a-olefin, and the Z-average molecular weight by gel permeation chromatography is 6,000,000 or more. And a polymer having a die swell ratio of 1.4 or more is prepolymerized in an amount of 0.01 to 1000 g per 1 g of the solid catalyst component.

  The third olefin polymerization catalyst according to the present invention comprises: (A) a transition metal compound belonging to Group 4 of the periodic table containing at least one ligand having a cyclopentadienyl skeleton on a solid carrier; The solid catalyst component obtained by contacting the oxy compound, the (C) polyfunctional organic halide and the (D) organoaluminum compound is contacted with ethylene or ethylene / a-olefin, and the Z average is determined by gel permeation chromatography. It is characterized in that a polymer having a molecular weight of 6,000,000 or more and a die swell ratio of 1.4 or more is prepolymerized in an amount of 0.01 to 1000 g per 1 g of the solid catalyst component.

  The olefin polymerization method according to the present invention is characterized in that olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst as described above.

  The olefin polymerization catalyst according to the present invention can produce an olefin polymer having excellent melt tension, small neck-in, excellent mechanical strength, and excellent particle properties with high polymerization activity.

  Hereinafter, the olefin polymerization catalyst according to the present invention and the olefin polymerization method using the olefin polymerization catalyst will be specifically described. In the present invention, the term "polymerization" is not limited to homopolymerization, but may be used in a sense that encompasses copolymerization, and the term "polymer" refers to not only homopolymers but also copolymers. Sometimes used in the inclusive sense.

  First, each component used in the olefin polymerization catalyst of the present invention will be described. The (A) transition metal compound of Group 4 of the periodic table containing one or more ligands having a cyclopentadienyl skeleton (hereinafter sometimes referred to as “component (A)”) used in the present invention is as follows. It is a transition metal compound represented by the following general formula (V).

MG ¹ _x ... (V)
(Wherein, M represents a transition metal atom selected from Group 4 of the periodic table, G represents a ligand coordinated to the transition metal, and at least one G ¹ has a cyclopentadienyl skeleton. G ¹ other than a ligand having a cyclopentadienyl skeleton is a hydrocarbon group, an alkoxy group, an aryloxy group, a trialkylsilyl group, an SO ₃ J group (where J is a substituent such as halogen). A hydrocarbon group having 1 to 8 carbon atoms which may have a halogen atom or a hydrogen atom, and x represents the valence of a transition metal.)
In the above general formula (V), M is a transition metal atom selected from Group 4 of the periodic table, specifically, a zirconium atom, a titanium atom or a hafnium atom, and preferably a zirconium atom.

  Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, Methylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopentadienyl Or an alkyl-substituted cyclopentadienyl group such as a hexylcyclopentadienyl group; or an indenyl group, 2-methylindenyl, 2-ethylindenyl group, 2-n-propylindenyl group, 2-phenylindenyl Group, 4-phenylindene Group, 2-methyl-4-phenylindenyl group, 2-methyl-4,6-dii-propylindenyl group, 2-methyl-4,5-benzoindenyl group, 4,5,6,7 -Tetrahydroindenyl, fluorenyl, 9-methylfluorenyl, 2,7-dimethylfluorenyl, 2,7-di-tert-butylfluorenyl and the like. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

  When the compound represented by the general formula (V) contains two or more ligands having a cyclopentadienyl skeleton, two of the ligands having a cyclopentadienyl skeleton are mutually methylene, Diisopropylmethylene, methyl-t-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, methylnaphthylmethylene, dinaphthylmethylene, ethylene, propylene, isopropylidene, cyclopropylidene, cyclobutylidene, cyclopentylidene , Cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindanilidene, chloroethylene group, chloromethylene group, silylene Methylsilylene, dimethylsilylene, diisopropylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, methylnaphthylsilylene, dinaphthylsilylene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetra Methylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene, and the above silicon-containing group may be bonded to germanium, a germanium-containing group in which tin is converted to tin, a tin-containing group, or the like. .

The ligand G ¹ other than the ligand having a cyclopentadienyl skeleton, specifically include those as follows. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. For example, the cycloalkyl group includes a cyclopentyl group, a cyclohexyl group and the like, the aryl group includes a phenyl group and a tolyl group, and the aralkyl group includes a benzyl group and a neophyl group.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the halogen include fluorine, chlorine, bromine, and iodine.

Examples of the ligand represented by SO ₃ J include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group. Such a transition metal compound containing a ligand having a cyclopentadienyl skeleton, for example, when the valence of the transition metal is 4, is more specifically represented by the following general formula (Va).
^{_{G 2 k G 3 l G 4}} m G 5 n M ... (Va)
(Wherein, M represents a transition metal atom selected from Group 4 of the periodic table, G ² represents a group (ligand) having a cyclopentadienyl skeleton, and G ³ , G ^4, and G ⁵ represent cycloalkyl. A group having a pentadienyl skeleton (ligand), an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, an SO ₃ J group, a halogen atom or a hydrogen atom, k is an integer of 1 or more, and k + 1 + m + n = 4.)
In the present invention, in the transition metal compound represented by the general formula (Va), at least one of G ³ , G ^4, and G ⁵ is a group (ligand) having a cyclopentadienyl skeleton, for example, G Compounds in which ² and G ³ are groups (ligands) having a cyclopentadienyl skeleton. In the case of such a compound, two groups (ligands) each having a cyclopentadienyl skeleton are mutually an alkylene group such as methylene, ethylene, propylene, diisopropylmethylene, methyl-t-butylmethylene, dicyclohexylmethylene, Substituted alkylene groups such as methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, methylnaphthylmethylene, dinaphthylmethylene, isopropylidene, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [ 3.3.1] Cycloalkylene groups such as nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene and dihydroindanilidene; and halogens such as chloroethylene and chloromethylene. Alkylene group, silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, methylnaphthylsilylene, dinaphthylsilylene, cyclodimethylenesilylene, cyclotrimethyl (Substituted) silylene groups such as methylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, and cycloheptamethylenesilylene; further, germanium-containing groups in which silicon is converted to germanium or tin in the above-mentioned silicon-containing groups; tin It may be bonded via a contained group or the like. When G ² and G ³ are groups (ligands) having a cyclopentadienyl skeleton, G ⁴ and G ⁵ are groups having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, An aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO ₃ J, a halogen atom or a hydrogen atom.

  In the present invention, among the transition metal compounds containing two or more groups (ligands) having such a cyclopentadienyl skeleton, the following components (a-1), (a-2) and (a) At least one component selected from -3) is preferably used.

  Component (a-1) and component (a-2) are transition metal compounds represented by general formulas (II) and (III), respectively.

[In the formulas (II) and (III), R ^{1 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₂ -C _{20 20} alkenyl groups, C ₆ -C ₂₀ aryl groups, and C ₇ -C ₂₀ arylalkyl groups, which can include silicon, halogen or germanium atoms; R ³ and R ⁴ , R ⁴ and R ⁵ and at least one of R ⁵ and R ⁶ may be bonded to each other to form a ring. R ⁷ is a divalent group bonding two ligands, and is a C _{1 to} C ₂₀ hydrocarbon group, a C _{1 to} C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, or a germanium or tin-containing group. Two substituents on the same carbon, silicon, germanium, and tin atoms may be bonded to each other to form a ring. t ¹ and t ² are each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ hydrocarbon group, a C _{1 to} C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, and a sulfur-containing group. , A nitrogen-containing group and a phosphorus-containing group. M is a transition metal selected from titanium, zirconium and hafnium. ].

In the general formulas (II) and (III), examples of the halogen atom as R ^{1 to} R ⁶ include chlorine, bromine, fluorine, and iodine atoms. Examples of the C _{1 to} C ₂₀ alkyl group include a methyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, octyl group, nonyl group, dodecyl group , eicosyl group, norbornyl group, adamantyl group and the like; cycloalkyl group of C ₃ -C _20, a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like; alkenyl groups C ₂ -C _20, vinyl group, propenyl group, cyclohexenyl group and the _like; aryl alkyl C 7 _{-C 20,} benzyl, phenylethyl, phenyl Pro Pill and the like; C _{6 to} C ₂₀ aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, Acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like can be mentioned.

Examples of the halogen-containing group as R ^{1 to} R ⁶ include the above-described alkyl group, cycloalkyl group, alkenyl group, arylalkyl group, and a group in which at least one hydrogen atom of the aryl group is substituted with an appropriate halogen atom. No.

  Examples of the silicon- or germanium-containing group include the above-described alkyl group, cycloalkyl group, alkenyl group, arylalkyl group, and a group in which one or more carbon atoms of the aryl group are substituted with a silicon or germanium atom.

R ^{1 to} R ⁶ may be the same or different from each other, and may be adjacent groups, that is, at least one of R ³ and R ⁴ , R ⁴ and R ^5, and R ⁵ and R ^6. The sets may be joined together to form a ring. Examples of such an indenyl group forming a ring include a 4,5-benzoindenyl group, a 5,6-benzoindenyl group, a 6,7-benzoindenyl group, an α-acenaphthoindenyl group and a carbon atom thereof. Alkyl substituents of the formulas 1 to 10 can be mentioned.

R ⁷ is a divalent group bonding two ligands, and among the C _{1 to} C ₂₀ hydrocarbon groups, alkylene groups such as methylene, ethylene, propylene, diisopropylmethylene, methyl-t A substituted alkylene group such as -butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, methylnaphthylmethylene, dinaphthylmethylene, isopropylidene, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, Cycloalkyl groups such as cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, and dihydroindanilidene; and C ₁ -C ₂₀ halogen-containing carbon. Examples of the hydride group include groups in which one or more hydrogen atoms of the above hydrocarbon group have been substituted with an appropriate halogen atom.

Examples of the C ₁ -C ₂₀ silicon-containing group include silylene, methylsilylene, dimethylsilylene, diisopropylsilylene, methyl-t-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, methylnaphthylsilylene, and dinaphthyl (Substituted) silylene groups such as silylene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene, and the like. Examples of germanium and tin-containing groups include: And a group in which silicon is converted to germanium or tin in the silicon-containing group.

t ¹ and t ² are each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ hydrocarbon group, a C _{1 to} C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, and a sulfur-containing group. , A nitrogen-containing group and a phosphorus-containing group. Examples of the halogen atom include chlorine, bromine, fluorine and iodine atoms, and examples of the C ₁ -C ₂₀ hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group. Groups, t-butyl group, n-hexyl group, alkyl group such as n-decyl group, phenyl group, 1-naphthyl group, aryl group such as 2-naphthyl group, aralkyl group such as benzyl group, and the like. Examples of the C ₁ -C ₂₀ halogen-containing hydrocarbon group include groups in which one or more hydrogen atoms in the above hydrocarbon group have been substituted with an appropriate halogen atom, such as a trifluoromethyl group. Examples of the silicon-containing group include a trimethylsilyl group and a dimethyl (t-butyl) silyl group, and examples of the oxygen-containing group include a methoxy group and an ethoxy group. Examples of the sulfur-containing group include a thiol group and a sulfonic acid group. And the like. Examples of the nitrogen-containing group include a dimethylamino group, and examples of the phosphorus-containing group include a phenylphosphine group. t ¹ and t ² may be the same or different from each other.

  Examples of the transition metal compounds represented by the general formulas (I) and (II) of the component (a-1) and the component (a-2) include, for example, JP-A-4-268308 and JP-A-5-306304. JP-A-6-100579, JP-A-6-157661, JP-A-6-184179, JP-A-6-345809, JP-A-7-149815, JP-A-7-188318 and JP-A-7-258321. And the like.

  Specific examples include ethylenebis (indenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, ethylenebis (tetrahydroindenyl) zirconium dichloride, ethylenebis (2-methyltetrahydroindenyl) zirconium dichloride, 3-propylenebis (indenyl) zirconium dichloride, 1,3-propylenebis (2-methylindenyl) zirconium dichloride, 1,3-propylenebis (tetrahydroindenyl) zirconium dichloride, 1,3-propylenebis (2-methyl Tetrahydroindenyl) zirconium dichloride, 1,2-propylenebis (indenyl) zirconium dichloride, 1,2-propylenebis (2-methylindenyl) zirconium dichloride Lido, 1,2-propylenebis (tetrahydroindenyl) zirconium dichloride, 1,2-propylenebis (2-methyltetrahydroindenyl) zirconium dichloride, 2,3-butylenebis (indenyl) zirconium dichloride, 2,3-butylenebis ( 2-methylindenyl) zirconium dichloride, 2,3-butylenebis (tetrahydroindenyl) zirconium dichloride, 2,3-butylenebis (2-methyltetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-methylindenyl) zirconium dichloride, dimethylsilylenebis ( -Methyl-4-ethylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-propylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis ( 2-methyl-4-naphthylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-anthracenylindenyl) zirconium dichloride, dimethylsilylenebis (2-methylbenz [e] indenyl) zirconium dichloride, dimethylsilylenebis (2-methylbenz [f] indenyl) zirconium dichloride, dimethylsilylenebis (2-ethylindenyl) zirconium dichloride, dimethylsilylenebis (2-ethyl-4-phenyli Ndenyl) zirconium dichloride, dimethylsilylenebis (2-ethylbenz [e] indenyl) zirconium dichloride, dimethylsilylenebis (2,5-dimethyl-4-methylindenyl) zirconium dichloride, dimethylsilylenebis (2,5-dimethyl-4) -Ethylindenyl) zirconium dichloride, dimethylsilylenebis (2,5-dimethyl-4-propylindenyl) zirconium dichloride, dimethylsilylenebis (2,5-dimethyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis ( 2,5-dimethyl-4-naphthylindenyl) zirconium dichloride, dimethylsilylenebis (2,5-dimethyl-4-anthracenylindenyl) zirconium dichloride, dimethylsilylenebis ( , 6-dimethyl-4-methylindenyl) zirconium dichloride, dimethylsilylenebis (2,6-dimethyl-4-ethylindenyl) zirconium dichloride, dimethylsilylenebis (2,6-dimethyl-4-propylindenyl) zirconium Dichloride, dimethylsilylenebis (2,6-dimethyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2,6-dimethyl-4-naphthylindenyl) zirconium dichloride, dimethylsilylenebis (2,6-dimethyl- 4-anthracenylindenyl) zirconium dichloride, dimethylsilylenebis (2,7-dimethyl-4-methylindenyl) zirconium dichloride, dimethylsilylenebis (2,7-dimethyl-4-ethylindenyl) zirconium Dichloride, dimethylsilylenebis (2,7-dimethyl-4-propylindenyl) zirconium dichloride, dimethylsilylenebis (2,7-dimethyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2,7-dimethyl- 4-naphthylindenyl) zirconium dichloride, dimethylsilylenebis (2,7-dimethyl-4-anthracenylindenyl) zirconium dichloride, phenylmethylsilylenebis (indenyl) zirconium dichloride, phenylmethylsilylenebis (2-methylindenyl ) Zirconium dichloride, phenylmethylsilylenebis (2-methyl-4-methylindenyl) zirconium dichloride, phenylmethylsilylenebis (2-methyl-4-ethylindenyl) zirconium Mudichloride, phenylmethylsilylenebis (2-methyl-4-propylindenyl) zirconium dichloride, phenylmethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, phenylmethylsilylenebis (2-methyl-4-naphthyl) (Indenyl) zirconium dichloride, phenylmethylsilylenebis (2-methyl-4-anthracenylindenyl) zirconium dichloride, phenylmethylsilylenebis (2-methylbenz [e] indenyl) zirconium dichloride, phenylmethylsilylenebis (2-methylbenz [F] indenyl) zirconium dichloride, phenylmethylsilylenebis (2-ethylindenyl) zirconium dichloride, phenylmethylsilylenebis (2-ethyl-4-fe Ruindenyl) zirconium dichloride, phenylmethylsilylenebis (2-ethylbenz [e] indenyl) zirconium dichloride, phenylmethylsilylenebis (2,5-dimethyl-4-methylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,5- Dimethyl-4-ethylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,5-dimethyl-4-propylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,5-dimethyl-4-phenylindenyl) zirconium dichloride Phenylmethylsilylenebis (2,5-dimethyl-4-naphthylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,5-dimethyl-4-anthracenylindenyl) Zirconium dichloride, phenylmethylsilylenebis (2,6-dimethyl-4-methylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,6-dimethyl-4-ethylindenyl) zirconium dichloride, phenylmethylsilylenebis (2 6-dimethyl-4-propylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,6-dimethyl-4-phenylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,6-dimethyl-4-naphthylindenyl) Zirconium dichloride, phenylmethylsilylenebis (2,6-dimethyl-4-anthracenylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,7-dimethyl-4-methylindenyl) zirconi Dimethyldichloride, phenylmethylsilylenebis (2,7-dimethyl-4-ethylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,7-dimethyl-4-propylindenyl) zirconium dichloride, phenylmethylsilylenebis (2 7-dimethyl-4-phenylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,7-dimethyl-4-naphthylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,7-dimethyl-4-anthracenylindole Nyl) zirconium dichloride and dibromide compounds, dialkyl compounds, diaralkyl compounds, disilyl compounds, dialkoxy compounds, dithiol compounds, disulfonic acid compounds, diamino compounds, diamino compounds of the above metallocene compounds Central metal of Sufin compound or the compounds include metallocene compounds is titanium or hafnium.

  Component (a-3) is a transition metal compound represented by the general formula (IV).

[In formula (IV), R ^{8 to} R ¹⁹ each independently represent a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ alkyl group, a C _{3 to} C ₂₀ cycloalkyl group, or a C _{2 to} C ₂₀ alkenyl group. , A C ₆ -C ₂₀ aryl group, and a C ₇ -C ₂₀ arylalkyl group, which may include a silicon, halogen or germanium atom, wherein adjacent substituents R ¹² -R ¹⁹ are bonded to each other To form a ring. R ⁷ is a divalent group that bonds two ligands, and is a C ₁ -C ₂₀ hydrocarbon group, a C ₁ -C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, or a germanium or tin-containing group. And two substituents on the same carbon, silicon, germanium, and tin atoms may combine with each other to form a ring. t ¹ and t ² are each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ hydrocarbon group, a C _{1 to} C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, and a sulfur-containing group. , A nitrogen-containing group and a phosphorus-containing group. M is a transition metal selected from titanium, zirconium and hafnium. ]
In the general formula (IV), examples of the halogen atom among R ^{8 to} R ¹⁹ include a chlorine, bromine, fluorine and iodine atom. Examples of the C _{1 to} C ₂₀ alkyl group include a methyl group, an ethyl group, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, octyl, nonyl, dodecyl, eicosyl , norbornyl group, an adamantyl group, a cycloalkyl group C ₃ -C _20, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, alkenyl groups C ₂ -C _20, vinyl group, propenyl group , cyclohexenyl _group, aryl alkyl group having C 7 _{-C 20,} benzyl, phenylethyl, phenylpropyl Etc., aryl groups of C ₆ -C _20, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, alpha-or β- naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, Acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like can be mentioned. Examples of the halogen-containing group among R ^{8 to} R ¹⁹ include the above-described alkyl group, cycloalkyl group, alkenyl group, arylalkyl group, and a group in which at least one hydrogen atom of the aryl group is substituted with an appropriate halogen atom. Is mentioned. Examples of the silicon- or germanium-containing group include the above-described alkyl group, cycloalkyl group, alkenyl group, arylalkyl group, and a group in which one or more carbon atoms of the aryl group are substituted with a silicon or germanium atom. R ^{8 to} R ¹⁹ may be the same or different from each other.

Further, at least one pair of adjacent groups of R ^{12 to} R ¹⁹ on the fluorene ring may be bonded to each other to form a ring. Examples of the fluorenyl group forming such a ring include a benzofluorenyl group, a dibenzofluorenyl group, an octahydrodibenzofluorenyl group, and an octamethyloctahydrodibenzofluorenyl group. R ⁷ , t ¹ and t ² are the same as defined in the general formulas (II) and (III), and the same groups can be exemplified.

  Specific examples of the transition metal compound (a-3) represented by the general formula (IV) include isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) ( 2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) ( Octamethyloctahydridodibenzfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium Dichloride, diphenylmethylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexyl Siliden (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) ( 3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, phenylmethyl Tilmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (3 , 6-Di-tert-butylfluorenyl) zirconium dichloride, phenylmethylmethylene (cyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl) ) (Fluorenyl) zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl) (octamethyloctahydridodibenzfluore) Nil) zirconium dichloride, diphenylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) ) Zirconium dichloride, diphenylmethylene (3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butylcyclopentadiene) ) (Octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylidene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexyl Den (3-tert-butylcyclopentadienyl) (octamethyloctahydridedibenzfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconi Dichloride, phenylmethylmethylene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butylcyclopentadienyl) (3 , 6-di-tert-butylfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, isopropylidene (3-tert- Butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride Chloride, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclopentane) Dienyl) (octamethyloctahydridedibenzfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5) -Methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert- Butylfluoren ) Zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylidene (3-tert-butyl-5-methylcyclopentane) Dienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (3- tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylidene (3-tert-butyl-5-methylcyclopentadienyl) (octamethyl Octa Hydride-dibenzfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5-methylcyclopentane) Dienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluoride) Nyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, and a dibromide compound of the above metallocene compound, Alkyl compounds, diaralkyl compounds, disilyl compounds, dialkoxy compounds, dithiol compounds, disulfonic acid compounds, diamino compounds, the central metal of the diphosphine compound or the compounds include metallocene compounds is titanium or hafnium.

  Among the transition metal compounds represented by the general formulas (II), (III) and (IV), preferred compounds are the transition metal compounds represented by the general formulas (II) and (III), and particularly preferred are It is a transition metal compound represented by the formula (II).

  The organoaluminum oxy compound (B) (hereinafter sometimes referred to as “component (B)”) used in the present invention may be a conventionally known alumoxane, and is exemplified in JP-A-2-78687. Or a benzene-insoluble organic aluminum oxy compound as described above.

Conventionally known alumoxanes can be produced, for example, by the following methods (1) to (3).
(1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of the above to react.
(2) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

  In the above method, alumoxane is recovered as a hydrocarbon solution. Further, the solvent or the unreacted organoaluminum compound may be removed from the recovered solution of the alumoxane by distillation, and the obtained alumoxane may be redissolved in the solvent.

  Specific examples of the organoaluminum compound used when preparing alumoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, tris-butylaluminum, trialkyl aluminum such as t-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum; Dialkyl such as aluminum bromide and diisobutylaluminum chloride Rumi halide diethyl aluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide; and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkyl aluminum and tricycloalkyl aluminum are particularly preferred. Further, as the organoaluminum compound used when preparing alumoxane, isoprenyl aluminum represented by the following general formula (VI) can also be used.
_{(I-C 4 H 9)} x Al y (C 5 H 10) z ... (VI)
(Where x, y, and z are positive numbers and z ≧ 2x).
The above-mentioned organoaluminum compounds are used alone or in combination.

  Solvents used for the preparation of alumoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, and cyclopentane , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, gasoline, kerosene, petroleum fractions such as light oil or the above aromatic hydrocarbons, aliphatic hydrocarbons, halides of alicyclic hydrocarbons, especially chlorine And hydrocarbons such as bromides. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

  The benzene-insoluble organoaluminum oxy compound that can be used in the present invention includes a method of contacting a solution of alumoxane with water or an active hydrogen-containing compound, or a method of contacting an organoaluminum compound with water as described above. Can be obtained by Such a benzene-insoluble organic aluminum oxy compound has an Al component soluble in benzene at 60 ° C. of 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, and is insoluble in benzene. Or it is hardly soluble.

  The above-mentioned organoaluminum oxy compound (B) is usually marketed or handled as a toluene solution. The organic aluminum oxy compound (B) used in the present invention may contain a small amount of an organic compound component of a metal other than aluminum.

  (C) (hereinafter sometimes referred to as “component (C)”) used in the present invention is a polyfunctional organic halide represented by the general formula (I).

[In the formula (I), R is an (o + p) -valent group containing at least one halogen atom, o and p are positive integers satisfying (o + p) ≧ 2, and Q ¹ and Q ² are —OH, —NH ₂ or —NLH (in —NLH, L represents a C ₁ -C ₂₀ hydrocarbon group, a C ₁ -C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group , A nitrogen-containing group or a phosphorus-containing group.), L and R, N and R, and N and N may be bonded together to form a ring. ]
In the general formula (I), among L in the substituted amino group represented by -NLH in Q ¹ and Q ² , examples of the halogen atom include chlorine, bromine, fluorine and iodine atoms, and C _{1 to} C ₂₀ Examples of the hydrocarbon group include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group and n-decyl group, and phenyl group. And aryl groups such as 1-naphthyl group and 2-naphthyl group, and aralkyl groups such as benzyl group.

Examples of the C ₁ -C ₂₀ halogen-containing hydrocarbon group include groups in which one or more of the hydrogen atoms in the above hydrocarbon group have been replaced with an appropriate halogen atom, such as a trifluoromethyl group. Examples of the silicon-containing group include a trimethylsilyl group and a dimethyl (t-butyl) silyl group, and examples of the oxygen-containing group include a methoxy group and an ethoxy group. Examples of the sulfur-containing group include a thiol group and a sulfonic acid group. And the like. Examples of the nitrogen-containing group include a dimethylamino group, and examples of the phosphorus-containing group include a phenylphosphine group.

  Specific examples of such a polyfunctional organic halide represented by the general formula (I) include an OH-R-OH type compound (the definition of R is the same as that of the general formula (I)); Catechol, 4-fluorocatechol, 3,4-difluorocatechol, 3,5-difluorocatechol, 3,6-difluorocatechol, 3,4,5-trifluorocatechol, 3,4,6-trifluorocatechol, tetrafluoro Catechol, 3- (trifluoromethyl) catechol, 4- (trifluoromethyl) catechol, 3,4-di (trifluoromethyl) catechol, 3,5-di (trifluoromethyl) catechol, 3,6-di ( Trifluoromethyl) catechol, 3,4,5-tri (trifluoromethyl) catechol, 3,4,6-tri (trifluoromethyl Le) catechol, tetra (trifluoromethyl) catechol, 2-fluororesorcin, 4-fluororesorcin, 5-fluororesorcin, 2,4-difluororesorcin, 2,5-fluororesorcin, 4,5-difluororesorcin, 4, 6-difluororesorcin, 5,6-difluororesorcin, 2,4,5-trifluororesorcin, 4,5,6-trifluororesorcin, tetrafluororesorcin, 2- (trifluoromethyl) resorcin, 4- (trifluoro Methyl) resorcin, 5- (trifluoromethyl) resorcin, 2,4-di (trifluoromethyl) resorcin, 2,5- (trifluoromethyl) resorcin, 4,5-di (trifluoromethyl) resorcin, 4, 6-di (trifluoromethyl) resorcinol, 5 6-di (trifluoromethyl) resorcin, 2,4,5-tri (trifluoromethyl) resorcin, 4,5,6-tri (trifluoromethyl) resorcin, tetra (trifluoromethyl) resorcin, 2-fluorohydroquinone , 3-fluorohydroquinone, 2,3-difluorohydroquinone, 2,5-difluorohydroquinone, 2,6-difluorohydroquinone, 2,3,5-trifluorohydroquinone, 2,3,6-trifluorohydroquinone, tetrafluorohydroquinone , 2- (trifluoromethyl) hydroquinone, 3- (trifluoromethyl) hydroquinone, 2,3-di (trifluoromethyl) hydroquinone, 2,5-di (trifluoromethyl) hydroquinone, 2,6-di (tri Fluoromethyl) hide Roquinone, 2,3,5-tri (trifluoromethyl) hydroquinone, 2,3,6-tri (trifluoromethyl) hydroquinone, tetra (trifluoromethyl) hydroquinone, 1,3-bis (2-hydroxyhexafluoroisopropyl ) Benzene, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzene, 2-fluoro-1,5-dihydroxynaphthalene, 3-fluoro-1,5-dihydroxynaphthalene, 4-fluoro-1,5-dihydroxynaphthalene, 2, 3-difluoro-1,5-dihydroxynaphthalene, 2,4-difluoro-1,5-dihydroxynaphthalene, 2,6-difluoro-1,5-dihydroxynaphthalene, 2,7-difluoro-1,5-dihydroxynaphthalene, 2,8- Difluoro-1,5 Dihydroxynaphthalene, 3,4-difluoro-1,5-dihydroxynaphthalene, 3,8-difluoro-1,5-dihydroxynaphthalene, 4,8-difluoro-1,5-dihydroxynaphthalene, 2,3,4-trifluoro-1,5 -Dihydroxynaphthalene, 2,3,6-trifluoro-1,5-dihydroxynaphthalene, 2,3,7-trifluoro-1,5-dihydroxynaphthalene, 2,3,8-trifluoro-1,5-dihydroxynaphthalene, 2 , 3,6,7-Tetrafluoro-1,5-dihydroxynaphthalene, hexafluoro-1,5-dihydroxynaphthalene, 1-fluoro-2,6-dihydroxynaphthalene, 3-fluoro-2,6-dihydroxynaphthalene, 4-fluoro- 2,6-dihydroxynaphthalene, 1 3-difluoro-2,6-dihydroxynaphthalene, 1,4-difluoro-2,6-dihydroxynaphthalene, 1,5-difluoro-2,6-dihydroxynaphthalene, 3,4-difluoro-2,6-dihydroxynaphthalene, 3,5- Difluoro-2,6-dihydroxynaphthalene, 4,5-difluoro-2,6-dihydroxynaphthalene, 1,3,4-trifluoro-2,6-dihydroxynaphthalene, 1,3,5-trifluoro-2,6-dihydroxynaphthalene, 3,4,5-trifluoro-2,6-dihydroxynaphthalene, 1,3,4,5-tetrafluoro-2,6-dihydroxynaphthalene, hexafluoro-2,6-dihydroxynaphthalene, 2,3,4,5 -Tetrafluorobiphenol, 2,2 ', 4,4'-tetraf Luoro 4,4'-biphenol, 2,2 ', 3,3', 4,4 ', 5,5', 6,6'-octafluoro-4,4'-biphenol, 4,4'-bis ( 2-hydroxyhexafluoroisopropyl) diphenyl, bis (2,3-difluoro-4-hydroxy) methane, bis (2,6-difluoro-4-hydroxy) methane, bis (3,5-difluoro-4-hydroxy) methane, bis ( Tetrafluoro-4-hydroxy) methane, 4,4'-bis (2-hydroxyhexafluoroisopropyl) diphenyl ether, 4,4'-isopropylidenebis (2,6-difluorophenol), tetrafluoroethylene glycol, hexa Fluoro-1,3-propane glycol, 2,2 ′, 3,3′-tetrafluoro-1,4-butanediol Octafluoro-1,4-butanediol, perfluoro-1,5-pentanediol, perfluoro-1,6-hexanediol, perfluoro-1,7-heptanediol, perfluoro-1,8-octanediol, and the OH-R- Compounds in which a fluorine atom of the OH compound is substituted with a bromine atom or a chlorine atom, etc.

Examples of the H ₂ N—R—NH ₂ compound (the definition of R is the same as in the general formula (I)) include 2-amino-3-fluoroaniline, 2-amino-4-fluoroaniline, and 2-amino-5-fluoro Aniline, 2-amino-3,4-difluoroaniline, 2-amino-3,5-difluoroaniline, 2-amino-3,6-difluoroaniline, 2-amino-3,4,5-trifluoroaniline, 2 -Amino-3,4,6-trifluoroaniline, 2-amino-tetrafluoroaniline, 2-amino-3- (trifluoromethyl) aniline, 2-amino-4- (trifluoromethyl) aniline, 2-amino -3,4-di (trifluoromethyl) aniline, 2-amino-3,5-di (trifluoromethyl) aniline, 2-amino-3,6-di (trifluoromethyl) Niline, 2-amino-3,4,5-tri (trifluoromethyl) aniline, 2-amino-3,4,6-tri (trifluoromethyl) aniline, 2-amino-tetra (trifluoromethyl) aniline, 3-amino-2-fluoroaniline, 3-amino-4-fluoroaniline, 3-amino-5-fluoroaniline, 3-amino-2,4-difluoroaniline, 3-amino-2,5-fluoroaniline, 3 -Amino-4,5-difluoroaniline, 3-amino-4,6-difluoroaniline, 3-amino-5,6-difluoroaniline, 3-amino-2,4,5-trifluoroaniline, 3-amino- 4,5,6-trifluoroaniline, 3-amino-tetrafluoroaniline, 3-amino-2- (trifluoromethyl) aniline, 3-amino 4- (trifluoromethyl) aniline, 3-amino-5- (trifluoromethyl) aniline, 3-amino-2,4-di (trifluoromethyl) aniline, 3-amino-2,5- (trifluoromethyl ) Aniline, 3-amino-4,5-di (trifluoromethyl) aniline, 3-amino-4,6-di (trifluoromethyl) aniline, 3-amino-5,6-di (trifluoromethyl) aniline , 3-amino-2,4,5-tri (trifluoromethyl) aniline, 3-amino-4,5,6-tri (trifluoromethyl) aniline, 3-amino-tetra (trifluoromethyl) aniline, -Amino-2-fluoroaniline, 4-amino-3-fluoroaniline, 4-amino-2,3-difluoroaniline, 4-amino-2,5-difluoroanili 4-amino-2,6-difluoroaniline, 4-amino-2,3,5-trifluoroaniline, 4-amino-2,3,6-trifluoroaniline, 4-amino-tetrafluoroaniline, -Amino-2- (trifluoromethyl) aniline, 4-amino-3- (trifluoromethyl) aniline, 4-amino-2,3-di (trifluoromethyl) aniline, 4-amino-2,5-di (Trifluoromethyl) aniline, 4-amino-2,6-di (trifluoromethyl) aniline, 4-amino-2,3,5-tri (trifluoromethyl) aniline, 4-amino-2,3,6 -Tri (trifluoromethyl) aniline, 4-amino-tetra (trifluoromethyl) aniline, 2-amino-6-fluorobenzylamine, 1,5-diamino-2-fur Lonaphthalene, 1,5-diamino-3-fluoronaphthalene, 1,5-diamino-4-fluoronaphthalene, 1,5-diamino-2,3-difluoronaphthalene, 1,5-diamino-2,4-difluoronaphthalene 1,5-diamino-2,6-difluoronaphthalene, 1,5-diamino-2,7-difluoronaphthalene, 1,5-diamino-2,8-difluoronaphthalene, 1,5-diamino-3,4- Difluoronaphthalene, 1,5-diamino-3,8-difluoronaphthalene, 1,5-diamino-4,8-difluoronaphthalene, 1,5-diamino-2,3,4-trifluoronaphthalene, 1,5-diamino -2,3,6-trifluoronaphthalene, 1,5-diamino-2,3,7-trifluoronaphthalene, 1,5-diamino-2 3,8-trifluoronaphthalene, 1,5-diamino-2,3,6,7-tetrafluoronaphthalene, 1,5-diamino-hexafluoronaphthalene, 2,6-diamino-1-fluoronaphthalene, 2,6 -Diamino-3-fluoronaphthalene, 2,6-diamino-4-fluoronaphthalene, 2,6-diamino-1,3-difluoronaphthalene, 2,6-diamino-1,4-difluoronaphthalene, 2,6-diamino -1,5-difluoronaphthalene, 2,6-diamino-3,4-difluoronaphthalene, 2,6-diamino-3,5-difluoronaphthalene, 2,6-diamino-4,5-difluoronaphthalene, 2,6 -Diamino-1,3,4-trifluoronaphthalene, 2,6-diamino-1,3,5-trifluoronaphthalene, 2,6- Diamino-3,4,5-trifluoronaphthalene, 2,6-diamino-1,3,4,5-tetrafluoronaphthalene, 2,6-diamino-hexafluoronaphthalene, 4-amino-4 ′-(N- Methylamino) -2,3,4,5-tetrafluorobiphenyl, 4-amino-4 ′-(N-methylamino) -2,2 ′, 4,4′-tetrafluorobiphenyl, 4-amino-4 ′ -(N-methylamino) -2,2 ', 3,3', 4,4 ', 5,5', 6,6'-octafluorobiphenyl, 2,2'-bis (trifluoromethyl) -4 , 4'-Diaminobiphenyl, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, bis (4-amino-2,3-difluorophenyl) Methane, bis (4-amino-2, -Difluorophenyl) methane, bis (4-amino-3,5-difluorophenyl) methane, bis (4-amino-tetrafluorophenyl) methane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane 2,2-bis [4- (4-aminophenyl)]-hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-bis (2-amino-hexafluoroisopropyl ) Diphenyl ether, 4,4′-isopropylidenebis (2,6-difluoroaniline), 2,4-diamino-6- (4-fluorophenyl) pyrimidine, 2,4-diamino-5-fluoroquinazoline, 4,4 '-Diaminooctafluorobiphenyl, tetrafluorosuccinamide, tetrafluoroethylenedi Mine, hexafluoro-1,3-propenediamine, 2,2 ′, 3,3′-tetrafluoro-1,4-butylenediamine, octafluoro-1,4-butylenediamine, decafluoro-1,5-pentene Diamine, perfluoro-1,6-hexenediamine, perfluoro-1,7-heptenediamine, perfluoro-1,8-octenediamine and the above-mentioned H ₂ N—R—NH ₂ compound were replaced with fluorine atoms with bromine atoms and chlorine atoms. And the like.

  Examples of the HLN-R-NLH type compound (the definitions of R and L are the same as those in the general formula (I)) include 3-fluoro-1,2-di (N-methylamino) benzene, 4-fluoro-1,2- Di (N-methylamino) benzene, 3,4-difluoro-1,2-di (N-methylamino) benzene, 3,5-difluoro-1,2-di (N-methylamino) benzene, 3,6 -Difluoro-1,2-di (N-methylamino) benzene, 3,4,5-trifluoro-1,2-di (N-methylamino) benzene, 3,4,6-trifluoro-1,2 -Di (N-methylamino) benzene, tetrafluoro-1,2-di (N-methylamino) benzene, 2-fluoro-1,3-di (N-methylamino) benzene, 4-fluoro-1,3 -Di (N-methylamino) benzene, 5-f Oro-1,3-di (N-methylamino) benzene, 2,4-difluoro-1,3-di (N-methylamino) benzene, 2,5-fluoro-1,3-di (N-methylamino ) Benzene, 4,5-difluoro-1,3-di (N-methylamino) benzene, 4,6-difluoro-1,3-di (N-methylamino) benzene, 5,6-difluoro-1,3 -Di (N-methylamino) benzene, 2,4,5-trifluoro-1,3-di (N-methylamino) benzene, 4,5,6-trifluoro-1,3-di (N-methyl Amino) benzene, tetrafluoro-1,3-di (N-methylamino) benzene, 2-fluoro-1,4-di (N-methylamino) benzene, 3-fluoro-1,4-di (N-methyl Amino) benzene, 2,3-difluoro-1, -Di (N-methylamino) benzene, 2,5-difluoro-1,4-di (N-methylamino) benzene, 2,6-difluoro-1,4-di (N-methylamino) benzene, 2, 3,5-trifluoro-1,4-di (N-methylamino) benzene, 2,3,6-trifluoro-1,4-di (N-methylamino) benzene, tetrafluoro-1,4-di (N-methylamino) benzene, 2-fluoro-1,5-di (N-methylamino) naphthalene, 3-fluoro-1,5-di (N-methylamino) naphthalene, 4-fluoro-1,5-di (N -Methylamino) naphthalene, 2,3-difluoro-1,5-di (N-methylamino) naphthalene, 2,4-difluoro-1,5-di (N-methylamino) naphthalene, 2,6-difluoro-1,5 - N-methylamino) naphthalene, 2,7-difluoro-1,5-di (N-methylamino) naphthalene, 2,8-difluoro-1,5-di (N-methylamino) naphthalene, 3,4-difluoro-1, 5-di (N-methylamino) naphthalene, 3,8-difluoro-1,5-di (N-methylamino) naphthalene, 4,8-difluoro-1,5-di (N-methylamino) naphthalene, 2,3 2,4-trifluoro-1,5-di (N-methylamino) naphthalene, 2,3,6-trifluoro-1,5-di (N-methylamino) naphthalene, 2,3,7-trifluoro-1,5 -Di (N-methylamino) naphthalene, 2,3,8-trifluoro-1,5-di (N-methylamino) naphthalene, 2,3,6,7-tetrafluoro-1,5-di (N- Methyl Mino) naphthalene, hexafluoro-1,5-di (N-methylamino) naphthalene, 4,4′-di (N-methylamino) -2,3,4,5-tetrafluorobiphenyl, 4,4′- Di (N-methylamino) -2,2 ′, 4,4′-tetrafluorobiphenyl, 4,4′-di (N-methylamino) -2,2 ′, 3,3 ′, 4,4 ′, 5,5 ', 6,6'-octafluorobiphenyl, bis (4- (N-methylamino) -2,3-difluorophenyl) methane, bis ((N-methylamino) -2,6-difluorophenyl) Methane, bis (4- (N-methylamino) -3,5-difluorophenyl) methane, bis (4- (N-methylamino) -tetrafluorophenyl) methane, 4,4′-bis (2- (N -Methylamino) -hexafluoroisopropyl) Diphenyl ether, tetrafluoroethylenediamine, hexafluoro-1,3-propenediamine, 2,2 ′, 3,3′-hexafluoro-1,4-butylenediamine, octafluoro-1,4-butylenediamine, decafluoro-1 , 5-pentenediamine, perfluoro-1,6-hexenediamine, perfluoro-1,7-heptenediamine, perfluoro-1,8-octenediamine, 1,2-di (N-methylamino) tetrafluoroethane, 1,3-di ( N-methylamino) hexafluoropropane, 1,4-di (N-methylamino) -2,2 ′, 3,3′-hexafluorobutane, 1,4-di (N-methylamino) -octafluorobutane 1,5-di (N-methylamino) -decafluoropentane, 1,6-di (N-methylamino -Perfluorohexane, 1,7-di (N-methylamino) -perfluoropentane, 1,8-di (N-methylamino) -perfluorooctane, 5-fluorouracil, 6-fluorouracil, 1-fluoroxanthine, 3-fluoroxanthine, 7-fluoroxanthine, 3-fluoroadenine, 5-fluoromethyluracil, 5-trifluoromethyluracil, 6-fluoromethyllauracil, 1-fluoromethylxanthine, 3-fluoromethylxanthine, 7-fluoro Examples thereof include methylxanthine, 3-fluoromethyladenine, and compounds in which a fluorine atom of the HLN-R-NLH type compound is substituted with a bromine atom or a chlorine atom.

Examples of the HO-R-NH _2- type compound [the definition of R is the same as in the general formula (I)] include 2-amino-3-fluorophenol, 2-amino-4-fluorophenol, 2-amino-3,4- Difluorophenol, 2-amino-3,5-difluorophenol, 2-amino-3,6-difluorophenol, 2-amino-3,4,5-trifluorophenol, 2-amino-3,4,6-triphenol Fluorophenol, 2-amino-tetrafluorophenol, 2-amino-3- (trifluoromethyl) phenol, 2-amino-4- (trifluoromethyl) phenol, 2-amino-3,4-di (trifluoromethyl ) Phenol, 2-amino-3,5-di (trifluoromethyl) phenol, 2-amino-3,6-di (trifluoromethyl) phenol, 2-amino-3,4,5-tri (trifluoromethyl) phenol, 2-amino-3,4,6-tri (trifluoromethyl) phenol, 2-amino-tetra (trifluoromethyl) phenol, 3- Amino-2-fluorophenol, 3-amino-4-fluorophenol, 3-amino-5-fluorophenol, 3-amino-2,4-difluorophenol, 3-amino-2,5-fluorophenol, 3-amino -4,5-difluorophenol, 3-amino-4,6-difluorophenol, 3-amino-5,6-difluorophenol, 3-amino-2,4,5-trifluorophenol, 3-amino-4, 5,6-trifluorophenol, 3-amino-tetrafluorophenol, 3-amino-2- (trifluoromethyl) phenyl Phenol, 3-amino-4- (trifluoromethyl) phenol, 3-amino-5- (trifluoromethyl) phenol, 3-amino-2,4-di (trifluoromethyl) phenol, 3-amino-2, 5- (trifluoromethyl) phenol, 3-amino-4,5-di (trifluoromethyl) phenol, 3-amino-4,6-di (trifluoromethyl) phenol, 3-amino-5,6-di (Trifluoromethyl) phenol, 3-amino-2,4,5-tri (trifluoromethyl) phenol, 3-amino-4,5,6-tri (trifluoromethyl) phenol, 3-amino-tetra (trimethyl Fluoromethyl) phenol, 4-amino-2-fluorophenol, 4-amino-3-fluorophenol, 4-amino-2,3-difluoro Enol, 4-amino-2,5-difluorophenol, 4-amino-2,6-difluorophenol, 4-amino-2,3,5-trifluorophenol, 4-amino-2,3,6-trifluoro Phenol, 4-amino-tetrafluorophenol, 4-amino-2- (trifluoromethyl) phenol, 4-amino-3- (trifluoromethyl) phenol, 4-amino-2,3-di (trifluoromethyl) Phenol, 4-amino-2,5-di (trifluoromethyl) phenol, 4-amino-2,6-di (trifluoromethyl) phenol, 4-amino-2,3,5-tri (trifluoromethyl) Phenol, 4-amino-2,3,6-tri (trifluoromethyl) phenol, 4-amino-tetra (trifluoromethyl) pheno , 5-amino-2-fluoro-1-hydroxynaphthalene, 5-amino-3-fluoro-1-hydroxynaphthalene, 5-amino-4-fluoro-1-hydroxynaphthalene, 5-amino-2,3-difluoro-1- Hydroxynaphthalene, 5-amino-2,4-difluoro-1-hydroxynaphthalene, 5-amino-2,6-difluoro-1-hydroxynaphthalene, 5-amino-2,7-difluoro-1-hydroxynaphthalene, 5-amino-2 , 8-Difluoro-1-hydroxynaphthalene, 5-amino-3,4-difluoro-1-hydroxynaphthalene, 5-amino-3,8-difluoro-1-hydroxynaphthalene, 5-amino-4,8-difluoro-1-hydroxynaphthalene , 5-amino-2,3,4-trifluoro-1 Hydroxynaphthalene, 5-amino-2,3,6-trifluoro-1-hydroxynaphthalene, 5-amino-2,3,7-trifluoro-1-hydroxynaphthalene, 5-amino-2,3,8-trifluoro-1 -Hydroxynaphthalene, 5-amino-2,3,6,7-tetrafluoro-1-hydroxynaphthalene, 5-amino-hexafluoro-1-hydroxynaphthalene, 2-amino-1-fluoro-6-hydroxynaphthalene, 2-amino -3-fluoro-6-hydroxynaphthalene, 2-amino-4-fluoro-6-hydroxynaphthalenenaphthalene, 2-amino-1,3-difluoro-6-hydroxynaphthalene, 2-amino-1,4-difluoro-6-hydroxynaphthalene, 2 -Amino-1,5-difluoro-6-hydroxy Naphthalene, 2-amino-3,4-difluoro-6-hydroxynaphthalene, 2-amino-3,5-difluoro-6-hydroxynaphthalene, 2-amino-4,5-difluoro-6-hydroxynaphthalene, 2-amino-1,3,4- Trifluoro-6-hydroxynaphthalene, 2-amino-1,3,5-trifluoro-6-hydroxynaphthalene, 2-amino-3,4,5-trifluoro-6-hydroxynaphthalene, 2-amino-1,3,4,5 -Tetrafluoro-6-hydroxynaphthalene, 2-amino-hexafluoro-6-hydroxynaphthalene, bis (4-amino-2,3-difluorophenyl) methane, bis (4-amino-2,6-difluorophenyl) methane, Bis (4-hydroxy3,5-difluorophenyl) methane Bis (4-hydroxytetrafluorophenyl) methane, 4,4′-bis (2-amino-hexafluoroisopropyl) diphenyl ether, 4,4′-isopropylidenebis (2,6-difluoroaniline), 3,5 -Bis (trifluoromethyl) benzamide oxime, 5- (trifluoromethyl) pyridine-2-alkoxyamide oxime, 2-amino-tetrafluoroethanol, 3-amino-hexafluoro-1-propanol, 4-amino-2,2 ', 3,3'-tetrafluoro-1-butanol, 4-amino-octafluoro-1-butanol, 5-amino-perfluoro-1-pentanol, 6-amino-perfluoro-1-hexanol, 7- Amino-perfluoro-1-heptanol, 8-amino-perfluoro-1-oct Cyclohexanol and the fluorine atoms of the HO-R-NH ₂ compound, a bromine atom, the compound was replaced by a chlorine atom.

  Examples of the HO-R-NLH type compound (the definitions of L and R are the same as those in formula (I)) include 2- (N-methylamino) -3-fluorophenol and 2- (N-methylamino) -4- Fluorophenol, 2- (N-methylamino) -3,4-difluorophenol, 2- (N-methylamino) -3,5-difluorophenol, 2- (N-methylamino) -3,6-difluorophenol , 2- (N-methylamino) -3,4,5-trifluorophenol, 2- (N-methylamino) -3,4,6-trifluorophenol, 2- (N-methylamino) -tetrafluoro Phenol, 3- (N-methylamino) -2-fluorophenol, 3- (N-methylamino) -4-fluorophenol, 3- (N-methylamino) -5-fluorophenol 3- (N-methylamino) -2,4-difluorophenol, 3- (N-methylamino) -2,5-fluorophenol, 3- (N-methylamino) -4,5-difluorophenol, 3- (N-methylamino) -4,6-difluorophenol, 3- (N-methylamino) -5,6-difluorophenol, 3- (N-methylamino) -2,4,5-trifluorophenol, -(N-methylamino) -4,5,6-trifluorophenol, 3- (N-methylamino) tetrafluorophenol, 4- (N-methylamino) -2-fluorophenol, 4- (N-methyl Amino) -3-fluorophenol, 4- (N-methylamino) -2,3-difluorophenol, 4- (N-methylamino) -2,5-difluorophenol, -(N-methylamino) -2,6-difluorophenol, 4- (N-methylamino) -2,3,5-trifluorophenol, 4- (N-methylamino) -2,3,6-triphenyl Fluorophenol, 4- (N-methylamino) tetrafluorophenol, 5- (N-methylamino) -2-fluoro-1-hydroxynaphthalene, 5- (N-methylamino) -3-fluoro-1-hydroxynaphthalene, 5 -(N-methylamino) -4-fluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2,3-difluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2,4-difluoro-1 -Hydroxynaphthalene, 5- (N-methylamino) -2,6-difluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2,7-difluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2,8-difluoro-1-hydroxynaphthalene, 5- (N-methylamino) -3,4-difluoro-1-hydroxynaphthalene, 5 -(N-methylamino) -3,8-difluoro-1-hydroxynaphthalene, 5- (N-methylamino) -4,8-difluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2,3, 4-trifluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2,3,6-trifluoro-1-hydroxynaphthalene, 5- (N-methylamino) -2,3,7-trifluoro-1- Hydroxynaphthalene, 5- (N-methylamino) -2,3,8-trifluoro-1-hydroxynaphthalene, 5- (N-methyla G) -2,3,6,7-tetrafluoro-1-hydroxynaphthalene, 5- (N-methylamino) hexafluoro-1-hydroxynaphthalene, 2- (N-methylamino) -1-fluoro-6-hydroxy Naphthalene, 2- (N-methylamino) -3-fluoro-6-hydroxynaphthalene, 2- (N-methylamino) -4-fluoro-6-hydroxynaphthalenenaphthalene, 2- (N-methylamino) -1,3 -Difluoro-6-hydroxynaphthalene, 2- (N-methylamino) -1,4-difluoro-6-hydroxynaphthalene, 2- (N-methylamino) -1,5-difluoro-6-hydroxynaphthalene, 2- (N- Methylamino) -3,4-difluoro-6-hydroxynaphthalene, 2- (N-methylamino) -3,5-diph Orol 6-hydroxynaphthalene, 2- (N-methylamino) -4,5-difluoro-6-hydroxynaphthalene, 2- (N-methylamino) -1,3,4-trifluoro-6-hydroxynaphthalene, 2- (N-methylamino) -1,3,5-trifluoro-6-hydroxynaphthalene, 2- (N-methylamino) -3,4,5-trifluoro-6-hydroxynaphthalene, 2- (N-methylamino) -1,3,4,5-tetrafluoro-6-hydroxynaphthalene, 2- (N-methylamino) hexafluoro-6-hydroxynaphthalene, bis (4- (N-methylamino) -2,3-difluorophenyl ) Methane, bis (4- (N-methylamino) -2,6-difluorophenyl) methane, bis (4-hydroxy3,5-difluorophenyl) Nyl) methane, bis (4-hydroxytetrafluorophenyl) methane, 4,4′-bis (2- (N-methylamino) hexafluoroisopropyl) diphenyl ether, 4,4′-isopropylidenebis (2,6-di Fluoroaniline), 2- (N-methylamino) tetrafluoroethanol, 3- (N-methylamino) hexafluoro-1-propanol, 4- (N-methylamino) -2,2 ′, 3,3 ′ -Tetrafluoro-1-butanol, 4- (N-methylamino) octafluoro-1-butanol, 5- (N-methylamino) perfluoro-1-pentanol, 6- (N-methylamino) perfluoro-1- Hexanol, 7- (N-methylamino) perfluoro-1-heptanol, 8- (N-methylamino) perfluoro- -Octanol, 2- (N-trifluoromethylamino) -3-fluorophenol, 2- (N-trifluoromethylamino) -4-fluorophenol, 2- (N-trifluoromethylamino) -3,4- Difluorophenol, 2- (N-trifluoromethylamino) -3,5-difluorophenol, 2- (N-trifluoromethylamino) -3,6-difluorophenol, 2- (N-trifluoromethylamino)- 3,4,5-trifluorophenol, 2- (N-trifluoromethylamino) -3,4,6-trifluorophenol, 2- (N-trifluoromethylamino) tetrafluorophenol, 3- (N- (Trifluoromethylamino) -2-fluorophenol, 3- (N-trifluoromethylamino) -4-fluoro Phenol, 3- (N-trifluoromethylamino) -5-fluorophenol, 3- (N-trifluoromethylamino) -2,4-difluorophenol, 3- (N-trifluoromethylamino) -2,5 -Fluorophenol, 3- (N-trifluoromethylamino) -4,5-difluorophenol, 3- (N-trifluoromethylamino) -4,6-difluorophenol, 3- (N-trifluoromethylamino) -5,6-difluorophenol, 3- (N-trifluoromethylamino) -2,4,5-trifluorophenol, 3- (N-trifluoromethylamino) -4,5,6-trifluorophenol, 3- (N-trifluoromethylamino) tetrafluorophenol, 4- (N-trifluoromethylamino) -2-f Orophenol, 4- (N-trifluoromethylamino) -3-fluorophenol, 4- (N-trifluoromethylamino) -2,3-difluorophenol, 4- (N-trifluoromethylamino) -2, 5-difluorophenol, 4- (N-trifluoromethylamino) -2,6-difluorophenol, 4- (N-trifluoromethylamino) -2,3,5-trifluorophenol, 4- (N-trifluorophenol (Fluoromethylamino) -2,3,6-trifluorophenol, 4- (N-trifluoromethylamino) tetrafluorophenol, 5- (N-trifluoromethylamino) -2-fluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -3-fluoro-1-hydroxynaphthalene, 5- (N-trifluoro (Oromethylamino) -4-fluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2,3-difluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2,4-difluoro- 1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2,6-difluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2,7-difluoro-1-hydroxynaphthalene, 5- ( N-trifluoromethylamino) -2,8-difluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -3,4-difluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino)- 3,8-difluoro-1-hydroxynaphthalene, 5- (N-trifur (Oromethylamino) -4,8-difluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2,3,4-trifluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino)- 2,3,6-trifluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2,3,7-trifluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2, 3,8-trifluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) -2,3,6,7-tetrafluoro-1-hydroxynaphthalene, 5- (N-trifluoromethylamino) hexafluoro Raw 1-hydroxynaphthalene, 2- (N-trifluoromethylamino) -1-fluoro-6-hydroxy Phthalene, 2- (N-trifluoromethylamino) -3-fluoro-6-hydroxynaphthalene, 2- (N-trifluoromethylamino) -4-fluoro-6-hydroxynaphthalenenaphthalene, 2- (N-trifluoromethyl Amino) -1,3-difluoro-6-hydroxynaphthalene, 2- (N-trifluoromethylamino) -1,4-difluoro-6-hydroxynaphthalene, 2- (N-trifluoromethylamino) -1,5-difluoro- 6-hydroxynaphthalene, 2- (N-trifluoromethylamino) -3,4-difluoro-6-hydroxynaphthalene, 2- (N-trifluoromethylamino) -3,5-difluoro-6-hydroxynaphthalene, 2- ( N-trifluoromethylamino) -4,5-difluoro-6-hydro Sinaphthalene, 2- (N-trifluoromethylamino) -1,3,4-trifluoro-6-hydroxynaphthalene, 2- (N-trifluoromethylamino) -1,3,5-trifluoro-6-hydroxy Naphthalene, 2- (N-trifluoromethylamino) -3,4,5-trifluoro-6-hydroxynaphthalene, 2- (N-trifluoromethylamino) -1,3,4,5-tetrafluoro-6 Hydroxynaphthalene, 2- (N-trifluoromethylamino) hexafluoro-6-hydroxynaphthalene, bis (4- (N-trifluoromethylamino) -2,3-difluorophenyl) methane, bis (4- (N- Trifluoromethylamino) -2,6-difluorophenyl) methane, bis (4-hydroxy3,5-difluorophenyl) Methane, bis (4-hydroxytetrafluorophenyl) methane, 4,4′-bis (2- (N-trifluoromethylamino) hexafluoroisopropyl) diphenyl ether, 4,4′-isopropylidenebis (2,6-di (Fluoroaniline), 2- (N-trifluoromethylamino) tetrafluoroethanol, 3- (N-trifluoromethylamino) hexafluoro-1-propanol, 4- (N-trifluoromethylamino) -2,2 ', 3,3'-tetrafluoro-1-butanol, 4- (N-trifluoromethylamino) octafluoro-1-butanol, 5- (N-trifluoromethylamino) perfluoro-1-pentanol, 6 -(N-trifluoromethylamino) perfluoro-1-hexanol, 7- (N-trifluoro (Oromethylamino) perfluoro-1-heptanol, 8- (N-trifluoromethylamino) perfluoro-1-octanol, and compounds in which the fluorine atom of the above-mentioned HO-R-NLH type compound is substituted with a bromine atom or a chlorine atom, and the like. .

Examples of the H ₂ N—R—NLH type compound (the definitions of L and R are the same as those in formula (I)) include 2- (N-methylamino) -3-fluoroaniline and 2- (N-methylamino) 4-fluoroaniline, 2- (N-methylamino) -3,4-difluoroaniline, 2- (N-methylamino) -3,5-difluoroaniline, 2- (N-methylamino) -3,6- Difluoroaniline, 2- (N-methylamino) -3,4,5-trifluoroaniline, 2- (N-methylamino) -3,4,6-trifluoroaniline, 2- (N-methylamino) tetra Fluoroaniline, 3- (N-methylamino) -2-fluoroaniline, 3- (N-methylamino) -4-fluoroaniline, 3- (N-methylamino) -5-fluoroaniline, 3- (N- Methyla (No) -2,4-difluoroaniline, 3- (N-methylamino) -2,5-fluoroaniline, 3- (N-methylamino) -4,5-difluoroaniline, 3- (N-methylamino) -4,6-difluoroaniline, 3- (N-methylamino) -5,6-difluoroaniline, 3- (N-methylamino) -2,4,5-trifluoroaniline, 3- (N-methylamino ) -4,5,6-trifluoroaniline, 3- (N-methylamino) tetrafluoroaniline, 4- (N-methylamino) -2-fluoroaniline, 4- (N-methylamino) -3-fluoro Aniline, 4- (N-methylamino) -2,3-difluoroaniline, 4- (N-methylamino) -2,5-difluoroaniline, 4- (N-methylamino) -2,6-difluoroa Niline, 4- (N-methylamino) -2,3,5-trifluoroaniline, 4- (N-methylamino) -2,3,6-trifluoroaniline, 4- (N-methylamino) tetrafluoro Aniline, 5-amino-2-fluoro-1- (N-methylamino) naphthalene, 5-amino-3-fluoro-1- (N-methylamino) naphthalene, 5-amino-4-fluoro-1- (N-methylamino ) Naphthalene, 5-amino-2,3-difluoro-1- (N-methylamino) naphthalene, 5-amino-2,4-difluoro-1- (N-methylamino) naphthalene, 5-amino-2,6-difluoro- 1- (N-methylamino) naphthalene, 5-amino-2,7-difluoro-1- (N-methylamino) naphthalene, 5-amino-2,8-difluoro -(N-methylamino) naphthalene, 5-amino-3,4-difluoro-1- (N-methylamino) naphthalene, 5-amino-3,8-difluoro-1- (N-methylamino) naphthalene, 5-amino -4,8-Difluoro-1- (N-methylamino) naphthalene, 5-amino-2,3,4-trifluoro-1- (N-methylamino) naphthalene, 5-amino-2,3,6-trifluoro- 1- (N-methylamino) naphthalene, 5-amino-2,3,7-trifluoro-1- (N-methylamino) naphthalene, 5-amino-2,3,8-trifluoro-1- (N-methyl Amino) naphthalene, 5-amino-2,3,6,7-tetrafluoro-1- (N-methylamino) naphthalene, 5-amino-hexafluoro-1- (N-methylamino Naphthalene, 2-amino-1-fluoro-6- (N-methylamino) naphthalene, 2-amino-3-fluoro-6- (N-methylamino) naphthalene, 2-amino-4-fluoro-6- (N-methylamino) Naphthalene naphthalene, 2-amino-1,3-difluoro-6- (N-methylamino) naphthalene, 2-amino-1,4-difluoro-6- (N-methylamino) naphthalene, 2-amino-1,5-difluoro-6 (N-methylamino) naphthalene, 2-amino-3,4-difluoro-6- (N-methylamino) naphthalene, 2-amino-3,5-difluoro-6- (N-methylamino) naphthalene, 2-amino-4,5 -Difluoro-6- (N-methylamino) naphthalene, 2-amino-1,3,4-trifluoro-6- (N- Butylamino) naphthalene, 2-amino-1,3,5-trifluoro-6- (N-methylamino) naphthalene, 2-amino-3,4,5-trifluoro-6- (N-methylamino) naphthalene, 2-amino-1 , 3,4,5-tetrafluoro-6- (N-methylamino) naphthalene, 2-amino-hexafluoro-6- (N-methylamino) naphthalene, 4-amino-4 '-(N-methylamino) -2,3,4,5-tetrafluorobiphenyl, 4-amino-4 '-(N-methylamino) -2,2', 4,4'-tetrafluorobiphenyl, 4-amino-4 '-(N -Methylamino) -2,2 ', 3,3', 4,4 ', 5,5', 6,6'-octafluorobiphenyl, (4-amino-2,3-difluorophenyl) (4- ( N-methylamino) -2,3-diflu (Phenyl) methane, (4-amino-2,6-difluorophenyl) (4- (N-methylamino) -2,6-difluorophenyl) methane, (4-amino-3,5-difluorophenyl) (4- (N-methylamino) -3,5-difluorophenyl) methane, (4-amino-tetrafluorophenyl) (4- (N-methylamino) -tetrafluorophenyl) methane, (4- (2-amino-hexa) Fluoroisopropyl)) (4- (4- (N-methylamino) -hexafluoroisopropyl)) diphenyl ether, 1-amino-2- (N-methylamino) tetrafluoroethane, 1-amino-3- (N-methyl Amino) -hexafluoropropane, 1-amino-4- (N-methylamino) -2,2 ′, 3,3′-hexafluorobutane, 1-amino 4- (N-methylamino) -octafluorobutane, 1-amino-5- (N-methylamino) -decafluoropentane, 1-amino-6- (N-methylamino) -perfluorohexane, 1-amino -7- (N-methylamino) -perfluoropentane, 1-amino-8- (N-methylamino) -perfluorooctane, (4-bromotetrafluorophenyl) hydrazine, 2-chloro-6-fluorophenylhydrazine, 3-chloro-4-fluorophenylhydrazine, 2-chloro-4- (trifluoromethyl) phenylhydrazine, 2-chloro-5-trifluoromethylphenylhydrazine, 2,4-dictoto 6- (trifluoromethyl) phenylhydrazine, 2, 6-dictoto 6- (trifluoromethyl) phenylhydrazine, 2,4- Fluorophenylhydrazine, 2,5-fluorophenylhydrazine, 5-fluoro-2-methylphenylhydrazine, 4-fluorophenylhydrazine, pentafluorophenylhydrazine, 4- (trifluoromethoxy) phenylhydrazine, 2- (trifluoromethyl) Examples thereof include phenylhydrazine, 2-amino-6-fluoro-purine, 2-amino-6-trifluoromethyl-purine, and compounds in which the fluorine atom of the above-mentioned H ₂ NR-NLH type compound is substituted with a bromine atom or a chlorine atom. .

  Of these, preferred are tetrafluororesorcin, tetrafluorohydroquinone, tetrabromohydroquinone, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzene, 4,4′-bis (2-hydroxyhexafluoroisopropyl) diphenyl, 4,4'-bis (2-hydroxyhexafluoroisopropyl) diphenyl ether, 2,2 ', 3,3'-tetrafluoro-1,4-butanediol, 2-amino-5-fluoroaniline, 2-amino-6 Fluorobenzylamine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 4,4'-diamino Octafluorobiphenyl, 2,2-bis (3-amino-4 Methylphenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenyl)]-hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4′-diaminooctafluoro Biphenyl, 5-trifluoromethyluracil and 4-amino-3-fluorophenol, particularly preferably tetrafluororesorcin, tetrafluorohydroquinone, tetrabromohydroquinone, 4,4′-diaminooctafluorobiphenyl, 2,2 ′ , 3,3'-Tetrafluoro-1,4-butanediol.

  As the organoaluminum compound (D) (hereinafter sometimes referred to as “component (D)”) used in the present invention, for example, an organoaluminum compound represented by the following general formula (VII) can be exemplified. .

^{_{R a n AlT 3-n ...}} (VII)
(In the formula, ^Ra is a hydrocarbon group having 1 to 12 carbon atoms, T is a halogen atom or a hydrogen atom, and n is 1 to 3.)
In the general formula (VII), ^Ra is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, Isopropyl, n-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, nonyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl, and the like.

  Specific examples of such an organoaluminum compound (D) include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; alkenyls such as isoprenylaluminum Aluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide; methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminumces Alkyl aluminum sesquihalides such as bromide; methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; dimethyl aluminum hydride, diethyl aluminum hydride, dihydrophenyl aluminum, diisopropyl aluminum hydride, di-n Alkyl aluminum hydrides such as -butyl aluminum hydride, diisobutyl aluminum hydride, diisohexyl aluminum hydride, diphenyl aluminum hydride, dicyclohexyl aluminum hydride, di-sec-heptyl aluminum hydride, di-sec-nonyl aluminum hydride and the like. It is.

  Further, as the organoaluminum compound (D), a compound represented by the following general formula (VIII) can also be used.

^{_{R a n AlU 3-n ...}} (VIII)
(Wherein, ^{R a} is as defined above, U is -OR ^b group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, ^-NR _{e 2} group, -SiR ^f ₃ group or -N ^(R g) a AlR ^h ₂ group, n is ^{1~2, R b, R c,} R d, and ^{R h} is like a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl radical, R ^e is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, and the like, and R ^f and R ^g are a methyl group, an ethyl group, and the like.)
As such an organoaluminum compound, specifically, the following compounds are used.
^{_{(1) R a n Al (}} OR b) a compound represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide; (2) R a n Al}} (OSiR c 3) 3 compounds represented by _-n, for example _{Et 2 Al (OSiMe 3),} (iso-Bu) 2 Al (OSiMe 3), such as _{(iso-Bu) 2 Al (} OSiEt 3); (3) R a n Al ( OAlR ^d ₂₎ a compound represented by _{3-n, e.g.,} Et ₂ AlOAlEt _2, (such as _{iso-Bu) 2 AlOAl (iso} -Bu) 2; (4) R a n Al (NR e) with _3-n compounds represented, for example, _{Me 2 AlNEt 2, Et 2 AlNHMe} , Me 2 AlNHEt, Et 2 AlN (SiMe 3) 2, (iso-Bu) 2 AlN ( etc. ^{_{iMe 3) 2; (5)}} R a n Al (SiR f 3) a compound represented by _3-n, for example (such as _{iso-Bu) 2 AlSiMe 3;} (6) R a n Al [N ^{(R g} ) ^AlR _{h 2]} A compound represented by _3-n, e.g., _{Et 2 AlN (Me) AlEt 2} , such as _{(iso-Bu) 2 AlN (} Et) Al (iso-Bu) 2.

Among the organoaluminum compounds represented by the general formula (VII) and (VIII), is preferably a compound represented by the general formula R ^{a 3} _Al, those R ^a is an alkyl group having 1 to 4 carbon atoms Is preferred.

In the olefin polymerization catalyst according to the present invention, each of the above components is supported on the following solid carrier. The solid carrier used in the present invention is an inorganic or organic compound, and a granular or particulate solid having a particle size of 3 to 300 μm, preferably 5 to 200 μm is used. Among them, the inorganic carrier is preferably a porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or the like, or , For example, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, and the like. be able to. Among them, those containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component are preferable. In addition, a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ , it may contain carbonates, sulfates, nitrates and oxide components such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O.

The properties of such a solid carrier vary depending on the kind and the production method, but the solid carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 800 m ² / g, It is desirable that the pore volume is 0.3 to 2.5 cm ³ / g. The solid carrier is used by firing at a temperature of 100 to 1000 ° C, preferably 150 to 700 ° C, if necessary.

The properties of such a solid carrier vary depending on the type and manufacturing method, but the solid carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 700 m ² / g, It is desirable that the pore volume is 0.3 to 2.5 cm ³ / g. The solid carrier is used by firing at a temperature of 100 to 1000 ° C, preferably 150 to 700 ° C, if necessary.

  Further, examples of the solid carrier that can be used in the present invention include a granular or particulate solid of an organic compound having a particle size of 3 to 300 μm. Examples of these organic compounds include (co) polymers mainly composed of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, and vinylcyclohexane and styrene. A polymer or copolymer produced as a main component can be exemplified.

  Hereinafter, the method for preparing the olefin polymerization catalyst of the present invention will be specifically described.

  The first olefin polymerization catalyst according to the present invention comprises, as a solid support, (A) a transition metal compound of Group 4 of the periodic table containing at least one ligand having a cyclopentadienyl skeleton; Contacting the solid catalyst component carrying an aluminum oxy compound with ethylene or ethylene / a-olefin, the Z average molecular weight by gel permeation chromatography is 6,000,000 or more, and the die swell ratio is 1.4 or more. Is characterized by being prepolymerized from 0.01 to 1000 g per 1 g of the solid catalyst component.

  The solid catalyst component used in the present invention can be prepared by mixing and contacting the component (A), the component (B) and the solid carrier in an inert hydrocarbon. The mixing order of the components at this time is arbitrary, but a preferred contacting order is, for example, a method in which the component (B) is mixed and contacted with the solid carrier, then the component (A) is contacted, ) And component (B) are mixed and then contacted with a solid carrier.

  The second olefin polymerization catalyst according to the present invention comprises: (A) a transition metal compound belonging to Group 4 of the periodic table, the solid support comprising at least one ligand having a cyclopentadienyl skeleton; The solid catalyst component obtained by contacting the oxy compound with the polyfunctional organic halide (C) is contacted with ethylene or ethylene / a-olefin, and the Z-average molecular weight determined by gel permeation chromatography is 6,000,000 or more. The polymer is characterized in that a polymer having a die swell ratio of 1.4 or more is prepolymerized in an amount of 0.01 to 1000 g per 1 g of the solid catalyst component.

The solid catalyst component used in the present invention can be prepared by mixing and contacting the component (A), the component (B), the component (C) and the solid support in an inert hydrocarbon. In this case, the order of mixing the components is arbitrary, but it is desirable to avoid mixing and contacting the components (A) and (C) directly. Such direct contact may cause decomposition and alteration of the component (A), and it is highly possible that the catalytic activity of the finally obtained olefin polymerization catalyst is significantly reduced. Preferred contact sequences include, for example,
(i) a method in which the component (B) is mixed and contacted with the solid carrier, then the component (A) is brought into contact with the solid carrier, and then the component (C) is brought into contact with the solid carrier.
(ii) a method in which the component (B) is mixed and contacted with the solid carrier, and then the component (C) is brought into contact with the component (A),
(iii) a method in which the component (A) and the component (B) are mixed and contacted first, and then the solid carrier and the component (C) are mixed and contacted,
(Iv) A method in which a solid carrier is brought into contact with the contact mixture of the component (B) and the component (C), and then the component (A) is mixed and brought into contact.
(V) a method of mixing and contacting the component (B) with the solid carrier, then contacting the component (A), then contacting the component (C), and then contacting the component (B) again;
(Vi) a method in which the component (B) is mixed and contacted with the solid carrier, then the component (C) is brought into contact, the component (B) is brought into contact again, and the component (A) is further brought into contact with the solid carrier.
(Vii) A method in which the component (A) and the component (B) are mixed and contacted first, then the solid carrier, the component (C), and the component (B) are again mixed and contacted.

  The third olefin polymerization catalyst according to the present invention comprises: (A) a transition metal compound belonging to Group 4 of the periodic table, the solid support comprising at least one ligand having a cyclopentadienyl skeleton; Gel permeation chromatography by contacting ethylene or ethylene / a-olefin with a solid catalyst component obtained by contacting an aluminum oxy compound, (C) a polyfunctional organic halide, and (D) an organoaluminum compound The polymer is characterized in that a polymer having a Z average molecular weight of 6,000,000 or more and a die swell ratio of 1.5 or more is prepolymerized in an amount of 0.01 to 1000 g per 1 g of the solid catalyst component.

  The solid catalyst component can be prepared by mixing and contacting the component (A), the component (B), the component (C), the component (D) and the solid support in an inert hydrocarbon. The order of mixing the components at this time is arbitrary, but it is desirable to avoid mixing and contacting the components (A) and (C) directly for the same reason as described above.

Preferred contact sequences include, for example,
(i) After the component (B) is mixed and contacted with the solid carrier, and then the component (A) is brought into contact with the solid carrier, the component (C), the component (D), or the component (C) and the component (D) are mixed. Contacting the contact mixture,
(ii) a method in which the component (B) is mixed and contacted with the solid carrier, then the component (C) is contacted, and then the component (A) or the component (D) is contacted.
(iii) First, the component (A) and the component (B) are mixed and contacted, and then the solid carrier, and then the component (C), the component (D), or the contact mixture of the component (C) and the component (D) are mixed. How to contact,
(iv) A method in which a solid carrier is brought into contact with the contact mixture of the component (B) and the component (C), and then the component (A) or the component (D) is mixed and brought into contact.

Regarding the method for preparing the solid catalyst component of the present invention, when the above components are mixed, the component (A) is used in an amount of 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 5 × 10 ⁻⁶ to 1 g per 1 g of the solid carrier. It is used in an amount of 2 × 10 ⁻⁴ mol, and the concentration of the component (A) is 10 ⁻⁵ to 10 ⁻² mol / l—solvent, preferably 5 × 10 ^{−5 to} 5 × 10 ⁻³ mol / l— Range of solvents. The component (B) has an atomic ratio (Al / transition metal) of aluminum (Al) derived from the component (B) to a transition metal derived from the component (A), and is preferably 10 to 1,000, and more preferably 50 to 500. Used in the amount of Component (C) is used in an amount of 0.01 to 5.0 mol, preferably 0.02 to 1.0 mol, more preferably 0.03 to 0.5 mol, per 1 mol of aluminum derived from component (B). Used in the amount of When the component (D) is used, the gram atomic ratio (Al-D / Al / D) of the aluminum atom (Al-D) in the component (D) and the aluminum atom (Al-B) in the component (B) is used. Al-B) in an amount of 0.01 to 2.0, preferably 0.02 to 1.0.
The mixing temperature at the time of mixing the above components is −50 to 150 ° C., preferably −20 to 120 ° C., and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes. Further, the mixing temperature may be changed during the mixing contact.

  In the method for preparing a solid catalyst component of the present invention, as one of preferred contact forms, component (B) and component (C) are mixed and contacted in advance in an inert hydrocarbon, and component (B) and component (C) are mixed. After preparing a solution containing the mixed contact product with the above, a method of bringing the solution into contact with other components is exemplified. In mixing and contacting the component (B) and the component (C), the concentration of the component (B) is in the range of 0.01 to 5 mol / l-solvent, preferably 0.1 to 3 mol / l-solvent. is there. Component (C) is used in an amount of 0.01 to 5.0 mol, preferably 0.02 to 1.0 mol, more preferably 0.03 to 0.5 mol, per 1 mol of aluminum derived from component (B). Is desirable. The mixing temperature at the time of mixing and contacting the component (B) and the component (C) is -90 to 150C, preferably -80C to 120C, and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes. It is.

  Specific examples of the inert hydrocarbon used for preparing the solid catalyst component of the present invention include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane and cyclohexane And alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

In the first solid catalyst component according to the present invention, the transition metal atom derived from the component (A), the solid carrier per ^{1g, 10} -4 ~5 × ^{10 -2} gram atom, preferably 5.0 × 10 ^{- The} aluminum atom derived from the component (B) is supported in an amount of ^{4 to} 2 × 10 ⁻² gram atoms and 10 ^{−4 to} 1.0 gram atoms, preferably 5 × 10 ^{−3 to} 5 × 10 ⁻¹ gram atoms. Is desirably supported.

The second solid catalyst component according to the present invention, the transition metal atom derived from the component (A), the solid carrier per ^{1g, 10} -4 ~5 × ^{10 -2} gram atom, preferably 5.0 × 10 ^{- The} aluminum atom derived from the component (B) is supported in an amount of ^{4 to} 2 × 10 ⁻² gram atoms and 10 ^{−4 to} 1.0 gram atoms, preferably 5 × 10 ^{−3 to} 5 × 10 ⁻¹ gram atoms. It is desirable that the component (C) is supported in an amount of 5 × 10 ^{−5 to} 5 × 10 ⁻² mol, preferably 10 ⁻⁵ to 10 ⁻² mol.

In the third solid catalyst component according to the present invention, the transition metal atom derived from the component (A) contains 5 × 10 ^{−5 to} 5 × 10 ⁻² gram atom, preferably 10 ⁻⁵ to 5 × 10 ⁻² gram atom per 1 g of the solid carrier. The aluminum atom derived from the component (B) and the component (D) is supported in an amount of 10 ⁻² gram atoms, and 10 ^{−3 to} 1.0 gram atom, preferably 5 × 10 ^{−3 to} 5 × 10 ⁻¹ gram. It is supported in the amount of atoms, and it is desirable that the component (C) is supported in an amount of 5 × 10 ^{−5 to} 5 × 10 ⁻² mol, preferably 10 ⁻⁵ to 10 ⁻² mol.

The olefin polymerization catalyst of the present invention is produced by pre-polymerizing ethylene and α-olefin in the presence of the solid catalyst component, and the Z-average molecular weight of the pre-polymer obtained by the pre-polymerization is determined by gel permeation chromatography. Is 6,000,000 or more, and the die swell ratio is 1.4 or more.
Here, α-olefin means propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene , 1-octadecene, 1-eicosene and the like. Of these, ethylene or a combination of ethylene and an α-olefin used in the polymerization of ethylene is particularly preferred. The polymerization system may be any of a batch system, a semi-continuous system, and a continuous system, and any method can be adopted from a slurry polymerization method, a gas phase polymerization method, a solution polymerization method, and the like. .

  Examples of the polymerization solvent used for carrying out slurry polymerization or solution polymerization include, for example, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, cyclopentane, cyclohexane and methylcyclohexane. Alicyclic hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and chloroform. These solvents may be used alone or as a mixture of two or more. Further, the olefin itself can be used as a solvent.

In the prepolymerization, the component (A) is used as a transition metal in an amount of 10 ^{-6 to} 5 × 10 ^-4 mol, preferably 5 × 10 ^-6 to 2 × 10 ^-4 mol, per 1 g of the solid carrier. The component (B) is used in an atomic ratio (Al / transition metal) of aluminum (Al) of the component (B) to the transition metal of the component (A) in an amount of 10 to 1000, preferably 50 to 500. . Component (C) is used in an amount of 0.01 to 5.0 mol, preferably 0.02 to 1.0 mol, more preferably 0.03 to 0.5 mol, per 1 mol of component (B). Can be When the component (D) is used, the atomic ratio (Al-D / Al) between the aluminum atom (Al-D) in the component (D) and the aluminum atom (Al-b) in the component (B) is used. In -B), it is used in an amount of 0.01 to 5.0, preferably 0.02 to 1.0.

The concentration in the pre-polymerization system using the transition metal compound (A) or the solid catalyst component formed from each component is usually 10 ⁻⁶ to 2 × 10 ⁻¹ mol / L in a ratio of transition metal / polymerization volume of 1 liter, More preferably, it is 5 × 10 ⁻⁵ to 10 ⁻¹ mol / l.

  The prepolymerization temperature is -20 to 90 ° C, preferably 0 to 80 ° C, the prepolymerization time is 0.5 to 100 hours, preferably about 1 to 80 hours, and the prepolymerization pressure is normal pressure to 10 MPa, Preferably, the pressure is from normal pressure to 5 MPa.

In the prepolymerization, an olefin similar to the olefin used in the polymerization described later is used, but an olefin containing ethylene as a main component is preferable.
As the prepolymerization catalyst, olefin may be introduced into an olefin polymerization catalyst suspension prepared using an inert hydrocarbon solvent, and the olefin polymerization catalyst formed in the inert hydrocarbon solvent is separated from the suspension. After that, the suspension may be suspended again in an inert hydrocarbon, and the olefin may be introduced into the resulting suspension.

  It is desirable that the prepolymerization produces an olefin polymer (prepolymer) in an amount of 0.01 to 1000 g, preferably 0.1 to 800 g, more preferably 0.2 to 500 g per 1 g of the solid carrier.

  The slurry concentration is preferably low in order to increase the molecular weight of the prepolymer obtained by prepolymerization, but from the viewpoint of productivity, the solid catalyst component per 1 L of the solvent is 0.5 to 500 g / ml, Preferably it is 1 to 400 g / ml.

  The preferable range of the Z-average molecular weight, which is one of the characteristics of the prepolymer obtained by the prepolymerization, is preferably from 6,000,000 to 100,000,000, and particularly preferably from 10,000,000 to 50,000,000. Further, the range of the die swell ratio which means the presence of long chain branch, which is another feature of the prepolymer, is preferably 1.4 or more and 5.0 or less, particularly preferably 1.7 or more and 3.0 or less. It is as follows.

The weight average molecular weight (Mw) and the Z average molecular weight (Mz) were calculated from molecular weight distribution curves obtained by a Waters model “Alliance GPC 2000” gel permeation chromatograph (high temperature size exclusion chromatograph). The operating conditions are as follows:
Equipment used and condition measuring equipment: Gel permeation chromatograph alliance GPC2000 (Waters)
Analysis software; Chromatography data system Empower (Waters)
Column: TSKgel GMH ₆ -HT x 2 + TSKgel GMH ₆ -HTL x 2
(7.5mm inner diameter x 30cm length, Tosoh Corporation)
Mobile phase; o-dichlorobenzene [= ODCB] (Wako Pure Chemicals special grade reagent)
Detector: Differential refractometer (built-in device)
Column temperature: 140 ° C
Flow rate: 1.0mL / min
Injection volume: 500 μL
Sampling time interval: 1 second Sample concentration: 0.15% (w / v)
Molecular Weight Calibration Monodisperse polystyrene (Tosoh Corporation) / molecular weight 495 to molecular weight 20.6 million The molecular weight distribution and various average molecular weights were calculated in terms of PE molecular weight according to the general-purpose calibration procedure described below. [Z. Crubisic, P. Rempp, H. Benoit, J. Polym. Sci., B5 , 753 (1967)]
The die swell ratio of the prepolymer obtained by the prepolymerization was determined by the following method.
(Preparation of measurement sample)
The obtained prepolymerized catalyst was subjected to melt-kneading by the following method in order to suppress variations in physical property values. 0.1% by weight of Irganox 1076 (Ciba Specialty Chemicals) and 0.1% by weight of Irgafos168 (Ciba Specialty Chemicals) were added as heat stabilizers to the obtained prepolymerization catalyst. The mixture was melt-kneaded at 50 ° C. and a rotation speed of 50 rpm for 5 minutes. Further, the pre-melt polymerization catalyst was cooled using a press molding machine manufactured by Shinto Metal Industry Co., Ltd. under the conditions of a cooling temperature of 20 ° C., a cooling time of 5 minutes, and a press pressure of 100 kg / cm ² .
[Measurement of die swell ratio (SR)]
The die swell ratio (SR) was measured using a capillary rheometer manufactured by Toyo Seiki Seisaku-sho, Ltd .: Capillograph 1B (barrel type 10 mmφ). After melting 10 g of the measurement sample at a temperature of 190 ° C. for 6 minutes, it was extruded at an extrusion rate of 5.0 mm / min using the capillaries shown in FIGS. Sampling was performed when the strand was extruded about 30 mm from the capillary outlet, and the sample was cooled at room temperature for 1 minute. The diameter of the strand was measured at any five points, and the average value was taken as the strand diameter. The value obtained by dividing the strand diameter by the capillary diameter (4.5 mm) was defined as the die swell ratio (SR).

  Next, the olefin polymerization method according to the present invention will be described. In the present invention, olefin polymerization is carried out in the presence of the olefin polymerization catalyst. The polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or a gas phase polymerization method.

  In the liquid phase polymerization method, the same inert hydrocarbon as used in the production of the olefin polymerization catalyst described above can be used as a solvent, or the olefin itself can be used as a solvent.

When the olefin polymerization is carried out using the olefin polymerization catalyst of the present invention, the above-mentioned catalyst is used as the concentration of the transition metal atom derived from the component (A) in the polymerization system as 10 ⁻⁶ to 2 × 10 ^{−. 2} mol / liter (polymerization volume), preferably it is desirable to be used in an amount of 5 × 10 ^-5 to ^10-2 mol / liter (polymerization volume). At this time, an organic aluminum oxy compound may be used if desired. The amount of the organic aluminum oxy compound used is desirably in the range of 0 to 500 mol per gram atom of the transition metal atom derived from the component (A).

  The olefin polymerization temperature is preferably in the range of −50 to 100 ° C., preferably 0 to 90 ° C. when performing the slurry polymerization method, and 0 to 250 ° C. when performing the liquid phase polymerization method. C, preferably in the range of 20 to 200C. When carrying out the gas phase polymerization method, the polymerization temperature is desirably in the range of 0 to 120 ° C, preferably 20 to 100 ° C. The polymerization pressure is from normal pressure to 10 MPa, preferably from normal pressure to 5 MPa, and the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions.

  The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Examples of the olefin that can be polymerized by the olefin polymerization catalyst of the present invention include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, and 4-olefin. Methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; a cyclic olefin having 5 to 20 carbon atoms, for example, cyclopentene, cycloheptene, norbornene , 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like. Can be. Further, styrene, vinylcyclohexane, diene and the like can be used.

  The bulk density of the obtained olefin polymer is 0.2 to 0.6 g / cc, particularly preferably 0.3 to 0.5 g / ml. The bulk density was determined in accordance with JIS K-6721.

  Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

The melt tension (MT), melt flow rate (MFR), density and LNR of the polymer were measured as described below.
[Melt tension (MT)]
It is determined by measuring the stress when the molten polymer is stretched at a constant speed. For the measurement, an MT measuring machine manufactured by Toyo Seiki Seisaku-sho, Ltd. was used. The conditions were a resin temperature of 190 ° C., a barrel diameter of 9.55 mmφ, an extrusion speed of 15 mm / min, a winding speed of 10 to 20 m / min, a nozzle diameter of 2.095 mmφ, and a nozzle length of 8 mm.
[Melt flow rate (MFR)]
It is a numerical value measured at 190 ° C. under a load of 2.16 kg according to the standard method of ASTM D-1238.
[density]
It was measured by a density gradient tube method.
[LNR]
The LNR is calculated by the same method as the neck-in amount when a measurement sample is formed into a film using a small slit die, and a polyethylene (trade name: Mirason M11) by a high-pressure radical polymerization method commercially available from Mitsui Chemicals, Inc. It is determined by the ratio with the amount of neck-in when the film is formed. The LNR is measured by an apparatus consisting of (a) a capillary rheometer, (b) a slit die, (c) a cooling roll, an air nozzle, and (d) a take-up roll.

  (A) The capillary rheometer serves to extrude the molten resin. As the capillary rheometer, a capillary rheometer manufactured by Toyo Seiki Seisaku-sho, Ltd .: Capillograph 1B (barrel system 10 mmφ) was used at a barrel temperature of 200 ° C. and a piston speed of 50 mm / min. The measurement sample used was 20 g per measurement, and the melting time was 6 minutes.

  (B) A drawing viewed from above the slit die is shown in FIG. 1, a drawing viewed from the lateral direction is shown in FIG. 2, and a cross-sectional view taken along AB is shown in FIG. The slit die is fixed under the barrel of the capillary rheometer via a fastening nozzle (1) and an adapter joined to the joint (1), and is heated to 200 ° C. using a plate heater ((3) in FIG. (Thermocouple insert).

  (C) FIG. 4 shows a front view of the cooling roll and the air nozzle, and FIG. 5 shows a horizontal view thereof. The cooling roll (4) and the air nozzle (5) were installed below the slit die, and were fixed so that the distance between the lower end of the slit die and the upper end of the cooling roll (4) was 10 mm. The air nozzle length is 26 cm, and air blowing holes having a diameter of 1 mm are provided at intervals of 5.5 mm. The cooling air flow rate was 50 l / min.

  The film of the measurement sample was formed by the above apparatus, and a film of 1.75 m to 1.95 m from the end of the film was sampled. The neck-in amount (C) of the measurement sample is determined by a value obtained by subtracting the film width of the sampled film from the die width (40 mm) of the slit die. The film width was measured at three arbitrary points, and the average value was used. Further, the neck-in amount (d) of polyethylene (trade name: Mirason M11) by a high-pressure radical polymerization method commercially available from Mitsui Chemicals, Inc. is also determined by the same method as described above. LNR is determined by the following equation.

                            LNR = C / D

Preparation of Solid Component (S1) Under nitrogen flow, 13 g (component E) of silica (SiO ₂ ) dried at 250 ° C. for 10 hours was suspended in 100 mL of toluene, and then cooled to 0 ° C. To this suspension, 52.6 mL of a toluene solution (1.75 mmol / mL in terms of Al atom) of methylalumoxane (component B: albemarle product) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 to 2 ° C. Subsequently, the mixture was reacted at 0 ° C. for 30 minutes, then heated to 95 ° C. over 1.5 hours, and reacted at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by decantation. After the solid component thus obtained was washed four times with toluene, toluene was added to prepare a toluene slurry of the solid component (S1). A part of the obtained solid component (S1) was sampled and the concentration was examined. As a result, the slurry concentration was 0.1216 g / mL, and the Al concentration was 0.575 mmol / mL.

Preparation of Solid Catalyst Component (X-1) 208 mL of toluene was placed in a 400 mL glass flask purged with nitrogen, and while stirring, the toluene slurry (8.0 g in terms of solid part) of the solid component (S1) prepared above was charged. I entered. Next, 126 mL of a toluene solution of ethylenebis (indenyl) zirconium dichloride (component A) (0.0015 mmol / mL in terms of Zr atom) was added dropwise over 7 minutes, and the mixture was reacted at room temperature for 2 hours. Thereafter, the supernatant was removed by decantation and washed once with toluene to obtain a 250 mL toluene slurry. Next, 150 mL of a toluene solution in which 1.377 g (component C) of tetrafluorohydroquinone was dissolved was charged over 10 minutes at room temperature, the temperature was raised to 40 ° C., and the reaction was performed for 30 minutes. Thereafter, the supernatant was removed by decantation and washed once with toluene to obtain a 250 mL toluene slurry. Furthermore, 150 mL of a toluene solution (0.253 mmol / mL in terms of Al atom) of methylalumoxane (albemar product; component B) was added dropwise over 10 minutes, and the temperature was raised to 40 ° C., followed by a reaction for 30 minutes. Thereafter, the supernatant was removed by decantation, washed three times with toluene and three times with decane, and 150 mL of decane was added to prepare a decane slurry of the solid catalyst component (X-1). When a part of the obtained decane slurry of the solid catalyst component (X-1) was sampled and the concentration was examined, the Zr concentration was 0.0892 mg / mL and the Al concentration was 11.2 mg / mL.

Preparation of Prepolymerization Catalyst Component (Q-1) 500 mL of purified heptane was placed in a 1-liter SUS autoclave, which had been sufficiently purged with nitrogen. In an ethylene atmosphere at 20 ° C., 0.375 mmol of triisobutylaluminum (component D) and the solid catalyst component (X-1) (0.0508 mmol in terms of zirconium atom) were charged in this order. The ethylene pressure was set to 0.78 MPa · G, polymerization was performed at 20 ° C. for 8 hours, and then the pressure was released, and the ethylene in the autoclave was replaced with nitrogen. The contents were transferred to a 1 L container sufficiently purged with nitrogen, washed three times with decane, and decane was added to prepare a decane slurry of the prepolymerization catalyst component (Q-1). A part of the obtained decane slurry of the prepolymerized catalyst component (Q-1) was sampled, and the slurry concentration and the amount of prepolymerization were examined. The amount was 31 g / g—the solid catalyst component, and the polymerization amount calculated from the slurry concentration was 118.6 g (the prepolymerization catalyst concentration at the end of the polymerization was calculated as 237.2 g / L). The polymer obtained by the prepolymerization was subjected to gel permeation chromatography measurement (GPC) and die swell ratio (SR) measurement. As a result, the Mw of the prepolymer was 91.4 × 10 ⁴ , and the Mz was 1152. It was 9 × 10 ⁴ and the SR was 1.8.

Polymerization sufficiently put a SUS autoclave refined heptane 500mL of 1-liter purged with nitrogen, and distribution of ethylene, the liquid phase and the gas phase were saturated with ethylene. Next, after the inside of the system was replaced with a hydrogen-ethylene mixed gas (hydrogen concentration: 0.83 vol%), 15 mL of 1-hexene, 0.375 mmol of triisobutylaluminum (component D), the prepolymerization catalyst component (Q -1) 1.5 g was charged in this order. The temperature was raised to 80 ° C., and polymerization was performed at 0.78 MPa · G for 270 minutes. The obtained polymer was dried under vacuum for 10 hours to obtain 50.8 g of an ethylene / 1-hexene copolymer.

[Preparation of measurement sample]
0.1% by weight of Irganox 1076 (Ciba Specialty Chemicals) and 0.1% by weight of Irgafos168 (Ciba Specialty Chemicals) were added as heat stabilizers to the obtained ethylene-based polymer. The mixture was melt-kneaded at 180 ° C. and a rotation speed of 50 rpm for 5 minutes. Further, the molten polymer was cooled using a press molding machine manufactured by Shinto Metal Industry Co., Ltd. under the conditions of a cooling temperature of 20 ° C., a cooling time of 5 minutes and a cooling pressure of 100 kg / cm ² .

  Table 1 shows the measurement results of the melt flow rate (MFR), density, melt tension (MT), and small neck-in ratio (LNR).

In the same manner as in Example 1, except that the polymerization time was changed to 150 minutes instead of the polymerization time of 270 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 36.9 g of an ethylene / 1-hexene copolymer.

[Preparation of measurement sample]
A measurement sample was prepared in the same manner as in Example 1. Table 1 shows the measurement results of the melt flow rate (MFR), density, melt tension (MT), and small neck-in ratio (LNR).

In the same manner as in Example 1 except that the polymerization time was changed to 90 minutes instead of the polymerization time of 270 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 23.6 g of an ethylene / 1-hexene copolymer.

[Preparation of measurement sample]
A measurement sample was prepared in the same manner as in Example 1. Table 1 shows the measurement results of the melt flow rate (MFR), density, melt tension (MT), and small neck-in ratio (LNR).

Polymerization sufficiently put a SUS autoclave refined heptane 500mL of 1-liter purged with nitrogen, and distribution of ethylene, the liquid phase and the gas phase were saturated with ethylene. Next, after the inside of the system was replaced with a hydrogen-ethylene mixed gas (hydrogen concentration: 0.54 vol%), 15 mL of 1-hexene, 0.375 mmol of triisobutylaluminum (component D), the prepolymerization catalyst component (Q -1) 1.5 g was charged in this order. The temperature was raised to 80 ° C., and polymerization was performed at 0.78 MPa · G for 195 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 59.6 g of an ethylene / 1-hexene copolymer.

[Preparation of measurement sample]
A measurement sample was prepared in the same manner as in Example 1. Table 1 shows the measurement results of the melt flow rate (MFR), density, melt tension (MT), and small neck-in ratio (LNR).

In Polymerization Example 4, except that the inter-110 minutes instead of polymerization time 195 min were performed in the same manner as in Example 1. The obtained polymer was vacuum-dried for 10 hours to obtain 37.5 g of an ethylene / 1-hexene copolymer.

[Preparation of measurement sample]
A measurement sample was prepared in the same manner as in Example 1. Table 1 shows the measurement results of the melt flow rate (MFR), density, melt tension (MT), and small neck-in ratio (LNR).

Preparation of Prepolymerization Catalyst Component (Q-2) In the preparation of the prepolymerization catalyst component (Q-1), instead of the solid catalyst component (X-3) (0.0508 mmol in terms of zirconium atom), the solid catalyst component (X- 3) A prepolymerization catalyst component (Q-2) was prepared in the same manner as in the prepolymerization catalyst component (Q-1) except that the amount was changed to 0.0254 mmol in terms of zirconium atoms. A part of the obtained decane slurry of the prepolymerized catalyst component (Q-2) was sampled, and the slurry concentration and the prepolymerized amount were examined. The slurry concentration was 0.1693 g / mL, and the prepolymerization per 1 g of the solid catalyst component was performed. The amount was 31 g / g—the solid catalyst component, and the polymerization amount calculated from the slurry concentration was 58.9 g (the prepolymerization catalyst concentration at the end of the polymerization was calculated to be 117.8 g / L). In addition, when gel permeation chromatography measurement (GPC) of the polymer obtained by the prepolymerization was performed, Mw of the prepolymer was 104.5 × 10 ⁴ and Mz of the polymer was 1176.5 × 10 ⁴ .

Polymerization sufficiently put a SUS autoclave refined heptane 500mL of 1-liter purged with nitrogen, and distribution of ethylene, the liquid phase and the gas phase were saturated with ethylene. Next, after the inside of the system was replaced with a hydrogen-ethylene mixed gas (hydrogen concentration: 0.55 vol%), 1-hexene 50 mL, triisobutylaluminum 0.375 mmol (component D), a prepolymerization catalyst component (Q -2) 1.5 g was charged in this order. The temperature was raised to 65 ° C., and polymerization was performed at 0.78 MPa · G for 240 minutes. The obtained polymer was dried under vacuum for 10 hours to obtain 29.7 g of an ethylene / 1-hexene copolymer.

[Preparation of measurement sample]
A measurement sample was prepared in the same manner as in Example 1. Table 1 shows the measurement results of the melt flow rate (MFR), density, melt tension (MT), and small neck-in ratio (LNR).

Polymerization sufficiently put a SUS autoclave refined heptane 500mL of 1-liter purged with nitrogen, and distribution of ethylene, the liquid phase and the gas phase were saturated with ethylene. Next, after the inside of the system was replaced with a hydrogen-ethylene mixed gas (hydrogen concentration: 0.15 vol%), 60 mL of 1-hexene, 0.375 mmol of triisobutylaluminum (component D), the prepolymerization catalyst component (Q -2) 1.5 g was charged in this order. The temperature was raised to 65 ° C., and polymerization was performed at 0.78 MPa · G for 120 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 55.9 g of an ethylene / 1-hexene copolymer.

[Preparation of measurement sample]
A measurement sample was prepared in the same manner as in Example 1. Table 1 shows the measurement results of the melt flow rate (MFR), density, melt tension (MT), and small neck-in ratio (LNR).

Preparation of Solid Component (S2) Under a nitrogen stream, 30 g of silica (SiO ₂ ) (component E) dried at 250 ° C. for 10 hours was suspended in 460 mL of toluene, and then cooled to 0 ° C. To this suspension, 140 mL of a toluene solution of methylalumoxane (Component B: Mitsui Chemicals) (1.52 mmol / mL in terms of Al atom) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 to 2 ° C. Subsequently, the mixture was reacted at 0 ° C. for 30 minutes, then heated to 95 ° C. over 1.5 hours, and reacted at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by decantation. After the solid component thus obtained was washed three times with toluene, toluene was added to prepare a toluene slurry of the solid component (S). A part of the obtained solid component (S) was sampled and the concentration was examined. The result was a slurry concentration: 0.1191 g / mL and an Al concentration: 0.604 mmol / mL.

Preparation of Solid Catalyst Component (X-2) 100 mL of toluene was charged into a nitrogen-purged 200 mL glass flask, and a toluene slurry (2.0 g in terms of solid part) of the solid component (S2) was charged with stirring. Next, 33.2 mL of a toluene solution of ethylene bis (indenyl) zirconium dichloride (component A) (0.001521 mmol / mL in terms of Zr atom) was added dropwise, and the mixture was reacted at room temperature for 2 hours. Thereafter, the supernatant was removed by decantation and washed three times with toluene to obtain a 100 mL toluene slurry. Next, 363.9 mg (component C) of tetrafluorohydroquinone was charged at room temperature, the temperature was raised to 40 ° C., and the reaction was performed for 30 minutes. Thereafter, the supernatant was removed by decantation and washed three times with toluene to obtain a 100 mL toluene slurry. Further, 50 mL of a toluene solution (0.202 mmol / mL in terms of Al atom) of methylalumoxane (albemar product; component B) was added dropwise over 10 minutes, and the temperature was raised to 40 ° C., followed by a reaction for 30 minutes. Thereafter, the supernatant was removed by decantation, washed three times with toluene and three times with decane, and 100 mL of decane was added to prepare a decane slurry of the solid catalyst component (X-2). When a part of the obtained decane slurry of the solid catalyst component (X-2) was sampled and the concentration was examined, the Zr concentration was 0.0348 mg / mL and the Al concentration was 4.29 mg / mL.

Preparation of Prepolymerization Catalyst 500 mL of purified heptane was placed in a 1-liter SUS autoclave whose internal volume had been sufficiently replaced with nitrogen, ethylene was passed through, and the liquid phase and the gas phase were saturated with ethylene. In an ethylene atmosphere at 20 ° C., 0.375 mmol of triisobutylaluminum (component D) and the solid catalyst component (X) prepared above (0.004 mmol in terms of zirconium atom) were charged in this order. The ethylene pressure was set to 0.78 MPa · G, prepolymerization was performed at 20 ° C. for 30 minutes, and then the pressure was released, and the ethylene in the autoclave was replaced with nitrogen.

Polymerization Then, hydrogen - ethylene mixed gas (hydrogen concentration: 0.55vol%) using, after purging the system, the addition of 1-hexene 10 mL, the temperature was raised to 80 ° C., 0.78 MPa · The polymerization was performed at G for 14 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 28.8 g of an ethylene / 1-hexene copolymer.

[Preparation of measurement sample]
A measurement sample was prepared in the same manner as in Example 1. Table 1 shows the measurement results of the melt flow rate (MFR), density, melt tension (MT), and small neck-in ratio (LNR).

Analysis of Prepolymer in Prepolymerization Catalyst Separately, a prepolymerization catalyst prepared under the same conditions as above was charged into a large amount of methanol, and a small amount of hydrochloric acid was added to perform demineralization treatment. Thereafter, the mixture was filtered with a glass filter and dried at 80 ° C. under reduced pressure to obtain 0.79 g of a prepolymer. As a result of gel permeation chromatography measurement, Mw of the prepolymer was 116.4 × 10 ⁴ and Mz was 1036.1 × 10 ⁴ .

Preparation of Solid Catalyst Component (X-3) 100 mL of toluene was placed in a 200-mL glass flask purged with nitrogen, and a toluene slurry (2.0 g in terms of solid part) of the solid component (S2) was charged with stirring. Next, 33.2 mL of a toluene solution of ethylene bis (indenyl) zirconium dichloride (component A) (0.001521 mmol / mL in terms of Zr atom) was added dropwise, and the mixture was reacted at room temperature for 2 hours. Thereafter, the supernatant was removed by decantation and washed three times with toluene to obtain a 100 mL toluene slurry. Next, 367.9 mg of tetrafluorohydroquinone (component C) was charged at room temperature, and the temperature was raised to 40 ° C., followed by a reaction for 30 minutes. Thereafter, the supernatant was removed by decantation and washed three times with toluene to obtain a 100 mL toluene slurry. Further, 50 mL of a toluene solution of trimethylaluminum (component B) (0.0404 mmol / mL in terms of Al atom) was added dropwise over 10 minutes, the temperature was raised to 40 ° C., and the reaction was performed for 30 minutes. Thereafter, the supernatant was removed by decantation, washed three times with toluene and three times with decane, and 100 mL of decane was added to prepare a decane slurry of the solid catalyst component (X-3). When a part of the obtained decane slurry of the solid catalyst component (X-3) was sampled and the concentration was examined, the Zr concentration was 0.0291 mg / mL and the Al concentration was 2.40 mg / mL.

Preparation of Prepolymerization Catalyst 500 mL of purified heptane was placed in a 1-liter SUS autoclave whose internal volume had been sufficiently replaced with nitrogen, ethylene was passed through, and the liquid phase and the gas phase were saturated with ethylene. In an ethylene atmosphere at 20 ° C., 0.375 mmol of triisobutylaluminum (component D) and the solid catalyst component (X) prepared above (0.004 mmol in terms of zirconium atom) were charged in this order. The ethylene pressure was set to 0.78 MPa · G, and prepolymerization was performed at 20 ° C. for 30 minutes. Thereafter, the pressure was released, and the ethylene in the autoclave was replaced with nitrogen.

Polymerization Then, hydrogen - ethylene mixed gas (hydrogen concentration: 0.55vol%) using, after purging the system, the addition of 1-hexene 10 mL, the temperature was raised to 80 ° C., 0.78 MPa · Polymerization was performed at G for 10 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 30.5 g of an ethylene / 1-hexene copolymer.

[Preparation of measurement sample]
A measurement sample was prepared in the same manner as in Example 1. Table 1 shows the measurement results of the melt flow rate (MFR), density, melt tension (MT), and small neck-in ratio (LNR).

Analysis of Prepolymer in Prepolymerization Catalyst Separately, a prepolymerization catalyst prepared under the same conditions as above was charged into a large amount of methanol, and a small amount of hydrochloric acid was added to perform demineralization treatment. Thereafter, the solution was filtered with a glass filter and dried at 80 ° C. under reduced pressure to obtain 0.62 g of a prepolymer. As a result of gel permeation chromatography measurement, Mw of the prepolymer was 116.4 × 10 ⁴ and Mz was 1036.1 × 10 ⁴ .

Preparation of Solid Catalyst Component (X-1) 50 mL of toluene was placed in a 200-mL glass flask purged with nitrogen, and stirred, and a toluene slurry of the solid component prepared according to the same formulation (reaction temperature and reaction time) as the solid component (S2) (2.0 g in terms of solid part, 7.46 mmol in terms of Al atom). Next, 33.9 mL of a toluene solution (0.0011 mmol / mL in terms of Zr atom) of ethylenebis (indenyl) zirconium dichloride (component A) was added dropwise over 15 minutes, and the mixture was reacted at room temperature for 2 hours. Thereafter, the supernatant was removed by decantation and washed three times with toluene to obtain a 100 mL toluene slurry. Next, 135.8 mg of tetrafluorohydroquinone (component C) was charged at room temperature, and the temperature was raised to 40 ° C., followed by a reaction for 30 minutes. Thereafter, the supernatant was removed by decantation and washed three times with toluene to obtain a 50 mL toluene slurry. Furthermore, 50 mL of a toluene solution (0.15 mmol / mL in terms of Al atom) of methylalumoxane (component B) was added dropwise at room temperature over 15 minutes, and the temperature was raised to 40 ° C., followed by a reaction for 30 minutes. Thereafter, the supernatant was removed by decantation, washed three times with toluene and three times with hexane, and 100 mL of decane was added to prepare a decane slurry of the solid catalyst component (X-1). A part of the obtained decane slurry of the solid catalyst component (X-1) was sampled and the concentration was examined. The result was a Zr concentration of 0.0263 mg / mL and an Al concentration of 3.61 mg / mL.

Preparation of Prepolymerization Catalyst 500 mL of purified heptane was placed in a 1-liter SUS autoclave whose internal volume had been sufficiently replaced with nitrogen, ethylene was passed through, and the liquid phase and the gas phase were saturated with ethylene. In an ethylene atmosphere at 20 ° C., 0.375 mmol of triisobutylaluminum (component D) and the solid catalyst component (X-1) prepared above (0.004 mmol in terms of zirconium atom) were charged in this order. The ethylene pressure was set to 0.78 MPa · G, and prepolymerization was performed at 20 ° C. for 30 minutes. Thereafter, the pressure was released, and the ethylene in the autoclave was replaced with nitrogen.

Polymerization Then, hydrogen - ethylene mixed gas (hydrogen concentration: 0.55vol%) using, after purging the system, the addition of 1-hexene 10 mL, the temperature was raised to 80 ° C., 0.78 MPa · Polymerization was performed at G for 20 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 35.6 g of an ethylene / 1-hexene copolymer.

[Preparation of measurement sample]
A measurement sample was prepared in the same manner as in Example 1. Table 1 shows the measurement results of the melt flow rate (MFR), density, melt tension (MT), and small neck-in ratio (LNR).

Analysis of prepolymer in prepolymerization catalyst Separately, the prepolymerization catalyst prepared under the same conditions as above was charged into a large amount of methanol, and a small amount of hydrochloric acid was added to perform demineralization treatment. Thereafter, the mixture was collected by filtration through a glass filter and dried at 80 ° C. under reduced pressure to obtain 0.70 g of a prepolymer. As a result of gel permeation chromatography measurement, Mw of the prepolymer was 111.2 × 10 ⁴ and Mz was 897.1 × 10 ⁴ .

[Comparative Example 1]
Preparation of solid catalyst component (X-5)
A nitrogen-substituted 200 mL glass flask was charged with 30.7 mL of toluene,
Under stirring, a toluene slurry (3.0 g in terms of solid part, 11.2 mmol in terms of Al atom) of the solid component prepared with the same formulation (reaction temperature / reaction time) as the solid component (S2) was charged and heated to 80 ° C. The temperature rose. Next, 45.1 mL of a toluene solution of ethylene bis (indenyl) zirconium dichloride (component A) (0.00124 mmol / mL in terms of Zr atom) was added dropwise over 20 minutes, and the mixture was reacted at 80 ° C. for 2 hours. Then, after cooling to room temperature, the supernatant was removed by decantation, washed three times with hexane, and 150 mL of decane was added to prepare a decane slurry of the solid catalyst component (X-5). When a part of the obtained decane slurry of the solid catalyst component (X-5) was sampled and the concentration was examined, the Zr concentration was 0.027 mg / mL and the Al concentration was 1.91 mg / mL.

Preparation of Prepolymerization Catalyst 500 mL of purified heptane was placed in a 1-liter SUS autoclave whose internal volume had been sufficiently replaced with nitrogen, ethylene was passed through, and the liquid phase and the gas phase were saturated with ethylene. In an ethylene atmosphere at 20 ° C., 0.375 mmol of triisobutylaluminum (component D) and the solid catalyst component (X-5) prepared above (0.003 mmol in terms of zirconium atom) were charged in this order. The ethylene pressure was set to 0.78 MPa · G, prepolymerization was performed at 20 ° C. for 30 minutes, and then the pressure was released, and the ethylene in the autoclave was replaced with nitrogen.

Polymerization Then, hydrogen - ethylene mixed gas (hydrogen concentration: 0.38vol%) using, after purging the system, the addition of 1-hexene 10 mL, the temperature was raised to 80 ° C., 0.78 MPa · Polymerization was performed at G for 5 minutes. The obtained polymer was vacuum-dried for 10 hours to obtain 40.4 g of an ethylene / 1-hexene copolymer.

[Preparation of measurement sample]
A measurement sample was prepared in the same manner as in Example 1. Table 1 shows the measurement results of the melt flow rate (MFR), density, melt tension (MT), and small neck-in ratio (LNR).

Analysis of Prepolymer in Prepolymerization Catalyst Separately, a prepolymerization catalyst prepared under the same conditions as above was charged into a large amount of methanol, and a small amount of hydrochloric acid was added to perform demineralization treatment. Then, it was filtered with a glass filter and dried at 80 ° C. under reduced pressure to obtain 0.69 g of a prepolymer. When gel permeation chromatography measurement was performed, the Mw of the prepolymer was 63.1 × 10 ⁴ and the Mz was 509.6 × 10 ⁴ .

4 is a view of a slit die for measuring a small test neck-in ratio according to the present invention as viewed from above. It is the drawing seen from the lateral direction of the same slit die. It is AB sectional drawing of a slit die same as the above. It is the drawing seen from the front of a cooling roll and an air nozzle. It is the figure seen from the lateral direction of the cooling roll and the air nozzle. It is the figure seen from the upper direction of the capillary rheometer for measuring a die-die swell ratio. It is the figure seen from the side of the same capillary rheometer.

Claims (7)

For solid carriers,
(A) a transition metal compound of Group 4 of the periodic table containing one or more ligands having a cyclopentadienyl skeleton;
(B) Contacting ethylene or ethylene / a-olefin with a solid catalyst component having an organoaluminum oxy compound supported thereon, the Z average molecular weight by gel permeation chromatography is 6,000,000 or more, and the die swell ratio is An olefin polymerization catalyst obtained by prepolymerizing a polymer having a molecular weight of 1.4 or more per 0.01 g of a solid catalyst component. For solid carriers,
(A) a transition metal compound of Group 4 of the periodic table containing one or more ligands having a cyclopentadienyl skeleton;
(B) an organic aluminum oxy compound,
(C) Contacting a solid catalyst component obtained by contacting with a polyfunctional organic halide with ethylene or ethylene / a-olefin, and having a Z-average molecular weight by gel permeation chromatography of 6,000,000 or more, and a die An olefin polymerization catalyst, wherein a polymer having a well ratio of 1.4 or more is prepolymerized in an amount of 0.01 to 1000 g per 1 g of a solid catalyst component. For solid carriers,
(A) a transition metal compound of Group 4 of the periodic table containing one or more ligands having a cyclopentadienyl skeleton;
(B) an organic aluminum oxy compound,
(C) a polyfunctional organic halide; (D) contacting a solid catalyst component obtained by contacting with an organoaluminum compound with ethylene or ethylene / a-olefin to have a Z-average molecular weight of 6,000,000 by gel permeation chromatography; An olefin polymerization catalyst, wherein a polymer having a die swell ratio of 1.4 or more is prepolymerized in an amount of 0.01 to 1000 g per 1 g of a solid catalyst component.
The catalyst for olefin polymerization according to any one of claims 1 to 3, wherein the polyfunctional organic halide (C) is a compound represented by the following general formula (I).

[In the formula (I), R is an (o + p) -valent group containing at least one halogen atom, o and p are positive integers satisfying (o + p) ≧ 2, and Q ¹ and Q ² are —OH, —NH ₂ or —NLH (in —NLH, L represents a C ₁ -C ₂₀ hydrocarbon group, a C ₁ -C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group , A nitrogen-containing group or a phosphorus-containing group). L and R, N and R, and N and N may be bonded to each other to form a ring. ] The transition metal compound (A) of Group 4 of the periodic table containing one or more ligands having a cyclopentadienyl skeleton is a compound represented by the following general formula (II), (III) or (IV). The olefin polymerization catalyst according to claim 1 or 2, wherein the catalyst is an olefin polymerization catalyst.

[In the formulas (II) and (III), R ^{1 to} R ⁶ each independently represent a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ alkyl group, a C ₃ -C ₂₀ cycloalkyl group, a C ₂ -C _{20 20} alkenyl groups, C ₆ -C ₂₀ aryl groups, and C ₇ -C ₂₀ arylalkyl groups, which can include silicon, halogen or germanium atoms; R ³ and R ⁴ , R ⁴ and R ⁵ and at least one of R ⁵ and R ⁶ may be bonded to each other to form a ring. R ⁷ is a divalent group that bonds two ligands, and is a C ₁ -C ₂₀ hydrocarbon group, a C ₁ -C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, or a germanium or tin-containing group. And two substituents on the same carbon, silicon, germanium, and tin atoms may combine with each other to form a ring. t ¹ and t ² are each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ hydrocarbon group, a C _{1 to} C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, and a sulfur-containing group. , A nitrogen-containing group and a phosphorus-containing group. M is a transition metal selected from titanium, zirconium and hafnium. ]

[In formula (IV), R ⁷ , t ¹ , t ² , and M are the same as defined in formula (II), and R ^{8 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ alkyl group, C ₃ -C ₂₀ cycloalkyl group, C ₂ -C ₂₀ alkenyl group, C aryl group ₆ -C ₂₀ or _C 7 arylalkyl group _{-C 20} silicon, halogen or germanium It may contain an atom, and adjacent substituents R ^{8 to} R ¹⁹ may combine with each other to form a ring. ]   A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 5.   The method for producing an olefin polymer according to claim 6, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.

Images