JP2005306989A - Solid catalyst for olefin polymerization and method for olefin polymerization using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a catalyst for olefin polymerization, which provides an olefin polymer having a high molecular weight in high activity. <P>SOLUTION: The catalyst for olefin polymerization is obtained by bringing an inactive hydrocarbon solution, in which a transition metal compound (A) of the group 4 of the periodic table containing one or more ligands having a cyclopentadienyl skeleton and a polyfunctional organic halide (C) are dissolved, into contact with a suspension containing a solid carrier and an organoaluminumoxy compound (B), and, if necessary, further bringing at least one or more compounds selected from an organoaluminumoxy compound (B) and an organoaluminum compound (D) to the suspension. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an olefin polymerization catalyst and an olefin polymerization method. More specifically, the present invention relates to an olefin polymerization catalyst capable of obtaining an olefin polymer having a high molecular weight with high activity, and olefin polymerization using the olefin polymerization catalyst. It is about the method.

  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. A vanadium-based catalyst is 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 organoaluminum oxy compound (alumoxane) is known. Examples of a method for producing an ethylene / olefin copolymer using a simple catalyst include, for example, JP-A-58-19309, JP-A-60-35005, JP-A-60-35006, and JP-A-60-35007. And JP-A-60-35008.

Further, JP-A-60-260602 and JP-A-60-130604 describe 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 method has been proposed.
JP 58-019309 A Japanese Unexamined Patent Publication No. 60-035005 Japanese Patent Laid-Open No. 60-035006 Japanese Patent Laid-Open No. 60-035007 Japanese Patent Laid-Open No. 60-035008 JP 60-260602 A JP 60-130604 A JP-A-6-172594 Japanese Patent Laid-Open No. 11-166083

  By the way, a molded article having excellent mechanical strength can be obtained from a polyolefin having a high molecular weight, and a component having a high molecular weight as proposed in JP-A-6-172594 and JP-A-11-166083. A polymer having a high melt tension can be obtained by introducing a small amount of. And as a method of polymerizing polyolefin with a high molecular weight using the above catalyst, there is a method of lowering the polymerization temperature. However, in such a method, energy loss in the manufacturing process is large, and the catalytic activity is remarkably reduced. Therefore, industrial productivity is extremely low, and it is difficult to say that it is practically effective means. Thus, with conventional catalysts, it has been difficult to polymerize polyolefins having a high molecular weight with high activity.

  As a result of intensive studies in view of such a situation, the present inventors have found that a suspension containing one or more ligands having a cyclopentadienyl skeleton in a suspension containing a solid carrier and an organoaluminum oxy compound (B). After subjecting the inert hydrocarbon solution in which the transition metal compound (A) and the polyfunctional organic halide (C) in the Table 4 group are dissolved together, an organoaluminum oxy compound (B) or an organic compound is added as necessary. The inventors have found that an olefin polymerization catalyst obtained by further contacting at least one compound selected from aluminum compounds (D) can polymerize an olefin polymer having a high molecular weight with high activity, thereby completing the present invention. It was.

  The present invention has been made in view of the above situation, and an object of the present invention is to provide an olefin polymerization catalyst from which an olefin polymer having a high molecular weight can be obtained with high activity. It is an object of the present invention to provide a method for polymerizing olefins using an industrial catalyst.

  The first olefin polymerization catalyst according to the present invention is a group 4 of the periodic table containing at least one ligand having a cyclopentadienyl skeleton in a suspension containing a solid carrier and an organoaluminum oxy compound (B). The transition metal compound (A) and the polyfunctional organic halide (C) are both brought into contact with an inert hydrocarbon solution dissolved therein.

  The second olefin polymerization catalyst according to the present invention is a group 4 of the periodic table containing at least one ligand having a cyclopentadienyl skeleton in a suspension containing a solid support and an organoaluminum oxy compound (B). An inert hydrocarbon solution in which the transition metal compound (A) and the polyfunctional organic halide (C) are both dissolved is contact-treated, and then selected from the organoaluminum oxy compound (B) or the organoaluminum compound (D). It is characterized by being obtained by further contacting two or more compounds.

  The transition metal compound belonging to Group 4 of the periodic table containing at least one ligand having a cyclopentadienyl skeleton (A) is, for example, a compound represented by the following formula (II), (III) or (IV): Can be mentioned.

[In the formulas (II), (III) and (IV), R ^{1 to} R ⁶ each independently represents a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ alkyl group, a C _{3 to} C ₂₀ cycloalkyl group, C ₂ -C ₂₀ alkenyl group, selected from arylalkyl group C ₆ -C ₂₀ aryl groups and _C 7 _{-C 20,,} may include silicon, halogen or germanium atom, R ³ and R ^4, At least one of R ⁴ and R ⁵ and R ⁵ and R ⁶ may be bonded to each other to form a ring. R ^{8 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a C _{1 to} C ₂₀ alkyl group, a C _{3 to} C ₂₀ cycloalkyl group, a C _{2 to} C ₂₀ alkenyl group, or a C _{6 to} C ₂₀ Selected from aryl groups and C ₇ -C ₂₀ arylalkyl groups, which may contain silicon, halogen or germanium atoms, and adjacent substituents from R ^{8 to} R ¹⁹ are bonded to each other to form a ring; Also good. R ⁷ is a divalent group that binds two ligands, and includes a C _{1 to} C ₂₀ hydrocarbon group, a C _{1 to} C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, germanium, or tin-containing 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 -C ₂₀ hydrocarbon group, a C ₁ -C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, or a sulfur-containing group. , A group selected from a nitrogen-containing group and a phosphorus-containing group. M is a transition metal selected from titanium, zirconium and hafnium. ]
As the (C) polyfunctional organic halide, a compound represented by the following formula (I) is used.

[In the formula (I), R is an (o + p) -valent group containing one or more halogen atoms, 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 to} C ₂₀ hydrocarbon group, a C _{1 to} C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, or a sulfur-containing group. , An arbitrary group selected from a nitrogen-containing group or a phosphorus-containing group), and L and R, N and R, and N and N may be bonded to each other to form a ring. ]

  The method for producing an olefin polymer according to the present invention is characterized in that an olefin is homopolymerized or copolymerized in the presence of any of the above olefin polymerization catalysts. By such a catalyst for olefin polymerization and a method for producing an olefin polymer, an olefin polymer having a high molecular weight can be obtained with high activity.

  The olefin polymerization catalyst according to the present invention can produce an olefin polymer having a high molecular weight with high activity.

  Hereinafter, the olefin polymerization solid catalyst of the present invention and the olefin polymerization method using the olefin polymerization solid catalyst will be specifically described. In the present invention, the term “polymerization” may be used in the meaning including not only homopolymerization but also copolymerization, and the term “polymer” refers not only to homopolymers but also to copolymers. Sometimes used in the inclusive sense.

  First, each component used in the solid catalyst for olefin polymerization of the present invention will be described. The transition metal compound of Group 4 of the periodic table (hereinafter sometimes referred to as “component (A)”) containing at least one ligand having a cyclopentadienyl skeleton (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)
(In the formula, 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, alkoxy group, aryloxy group, trialkylsilyl group, 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 the transition metal.)

  In the 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, preferably a zirconium atom or a hafnium atom. Particularly preferred is a zirconium atom.

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

  When the compound represented by the general formula (V) includes two or more ligands having a cyclopentadienyl skeleton, the ligands having two cyclopentadienyl skeletons are 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 in the silicon-containing group, silicon may be bonded via germanium, a germanium-containing group obtained by converting tin into tin, a tin-containing group, or the like. .

Specific examples of the ligand G ¹ other than the ligand having a cyclopentadienyl skeleton include the following. 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. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aryl group include a phenyl group and a tolyl group. Examples of the aralkyl group include a benzyl group and a neophyll 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-toluenesulfonate group, a methanesulfonate group, a trifluoromethanesulfonate group, and the like. The transition metal compound containing a ligand having such a cyclopentadienyl skeleton is more specifically represented by the following general formula (Va) when the valence of the transition metal is 4, for example.

G ² _k G ³ _l G ⁴ _m G ⁵ _n M (Va)
(In the formula, 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 cyclo A group having a pentadienyl skeleton (ligand), alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, trialkylsilyl group, SO ₃ J group, halogen atom or hydrogen atom; k is an integer of 1 or more, and k + l + m + n = 4.)

In the present invention, in the transition metal compound represented by the general formula (Va), a compound in which at least one of G ³ , G ⁴ and G ⁵ is a group (ligand) having a cyclopentadienyl skeleton, such as G Examples thereof include compounds in which ² and G ³ are groups (ligands) having a cyclopentadienyl skeleton. In the case of such a compound, two of the groups (ligands) having a cyclopentadienyl skeleton are each 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, cyclotri (Substituted) silylene groups such as methylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene, and germanium-containing groups obtained by converting silicon into germanium and tin in the silicon-containing groups, tin It may be bonded via a containing group or the like. When G ² and G ³ are a group (ligand) having a cyclopentadienyl skeleton, G ⁴ and G ⁵ are a group 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 component (A-1), component (A-2) and component (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.

Wherein (II) and (III), R ¹ ~R ⁶ each independently represent a hydrogen atom, a halogen _atom, an alkyl group of C 1 _{-C 20,} cycloalkyl group of C ₃ ~C _20, C ₂ ~C _{It is selected from 20} alkenyl groups, C ₆ -C ₂₀ aryl groups, and C ₇ -C ₂₀ arylalkyl groups, and may contain 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 binds two ligands, and includes a C _{1 to} C ₂₀ hydrocarbon group, a C _{1 to} C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, germanium, or tin-containing 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 -C ₂₀ hydrocarbon group, a C ₁ -C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, or a sulfur-containing group. , A group selected from 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, etc .; as C ₃ -C ₂₀ cycloalkyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc .; as C ₂ -C ₂₀ alkenyl group, vinyl group, propenyl Groups, cyclohexenyl groups, etc .; C ₇ -C ₂₀ arylalkyl groups such as benzyl, phenylethyl, phenylpro Such as pills; as C ₆ -C ₂₀ aryl groups, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, Examples include acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like.

Examples of the halogen-containing group as R ^{1 to} R ⁶ include an alkyl group, a cycloalkyl group, an alkenyl group, an arylalkyl group, and a group in which one or more hydrogen atoms of the aryl group are substituted with an appropriate halogen atom. Can be mentioned.

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

R ^{1 to} R ⁶ may be the same as or different from each other, and at least one of adjacent groups, ie, R ³ and R ⁴ , R ⁴ and R ^5, and R ⁵ and R ^6. The sets may be bonded to each other to form a ring. Examples of the indenyl group forming such a ring include 4,5-benzoindenyl group, 5,6-benzoindenyl group, 6,7-benzoindenyl group, α-acenaphthoindenyl group and carbon thereof. Examples thereof include alkyl substituted products of 1 to 10.

R ⁷ is a divalent group that binds two ligands, of which C ₁ -C ₂₀ hydrocarbon groups include alkylene groups such as methylene, ethylene, propylene, diisopropylmethylene, methyl-t -Substituted alkylene groups such as butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, methylnaphthylmethylene, dinaphthylmethylene, isopropylidene, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, And cycloalkylene groups such as cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindanilidene, and the like, and C ₁ -C ₂₀ halogen-containing carbon. Examples of the hydride group include groups in which one or more hydrogen atoms of the hydrocarbon group are 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, dinaphthyl. (Substituted) silylene groups such as silylene, cyclodimethylene silylene, cyclotrimethylene silylene, cyclotetramethylene silylene, cyclopentamethylene silylene, cyclohexamethylene silylene, cycloheptamethylene silylene, and the like, germanium, tin-containing groups as In the silicon-containing group, a group obtained by converting silicon into germanium or tin can be used.

t ¹ and t ² are each independently a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ hydrocarbon group, a C ₁ -C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, or a sulfur-containing group. , A group selected from a nitrogen-containing group and a phosphorus-containing group. Examples of the halogen atom include chlorine, bromine, fluorine, and iodine atoms. Examples of the C _{1 to} 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. Group, alkyl group such as t-butyl group, n-hexyl group and n-decyl group, aryl group such as phenyl group, 1-naphthyl group and 2-naphthyl group, aralkyl group such as benzyl group, etc. Examples of the C _{1 to} C ₂₀ halogen-containing hydrocarbon group include a group in which one or more of the hydrogen atoms in the hydrocarbon group are substituted with an appropriate halogen atom, such as a trifluoromethyl group. Examples of the silicon-containing group include a trimethylsilyl group and dimethyl (t-butyl) silyl group. 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. 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 as or different from each other.

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

  Specific examples include ethylene bis (indenyl) zirconium dichloride, ethylene bis (2-methylindenyl) zirconium dichloride, ethylene bis (tetrahydroindenyl) zirconium dichloride, ethylene bis (2-methyltetrahydroindenyl) zirconium dichloride, 1, 3-propylene bis (indenyl) zirconium dichloride, 1,3-propylene bis (2-methylindenyl) zirconium dichloride, 1,3-propylene bis (tetrahydroindenyl) zirconium dichloride, 1,3-propylene bis (2-methyl) Tetrahydroindenyl) zirconium dichloride, 1,2-propylenebis (indenyl) zirconium dichloride, 1,2-propylenebis (2-methylindenyl) zirconium dichloride 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-phenyl) 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, dimethylsilylene bis (2,5-dimethyl-4-propylindenyl) zirconium dichloride, dimethylsilylene bis (2,5-dimethyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene bis ( 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) Luindenyl) 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, phenylmethylsilylene bis (2,6-dimethyl-4-methylindenyl) zirconium dichloride, phenylmethylsilylene bis (2,6-dimethyl-4-ethylindenyl) zirconium dichloride, phenylmethylsilylene bis (2, 6-dimethyl-4-propylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,6-dimethyl-4-phenylindenyl) zirconium dichloride, phenylmethylsilylenebis (2,6-dimethyl-4-naphthylindenyl) Zirconium dichloride, phenylmethylsilylene bis (2,6-dimethyl-4-anthracenylindenyl) zirconium dichloride, phenylmethylsilylene bis (2,7-dimethyl-4-methylindenyl) zirconi Um dichloride, 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-anthracenylindene) 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 general formula (IV).

[In the formula (IV), R ^{8 to} R ¹⁹ are each independently 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. , C ₆ -C ₂₀ aryl groups, and C ₇ -C ₂₀ arylalkyl groups, which may contain silicon, halogen or germanium atoms, and adjacent substituents from R ^{12 to} R ¹⁹ are bonded to each other To form a ring. R ⁷ is a divalent group that binds two ligands, and includes a C _{1 to} C ₂₀ hydrocarbon group, a C _{1 to} C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, germanium, or tin-containing 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 -C ₂₀ hydrocarbon group, a C ₁ -C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, or a sulfur-containing group. , A group selected from 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 in R ^{8 to} R ¹⁹ include chlorine, bromine, fluorine, and iodine atoms. Examples of the C _{1 to} C ₂₀ alkyl group include a methyl group, an 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, iconicyl group , Norbornyl group, adamantyl group, etc. as C ₃ -C ₂₀ cycloalkyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group etc. as C ₂ -C ₂₀ alkenyl group, 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, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like can be mentioned. Examples of the halogen-containing group among R ^{8 to} R ¹⁹ include the above alkyl group, cycloalkyl group, alkenyl group, arylalkyl group, a group in which one or more hydrogen atoms of the aryl group are substituted with an appropriate halogen atom, etc. Is mentioned. Examples of the silicon or germanium-containing group include alkyl groups, cycloalkyl groups, alkenyl groups, arylalkyl groups, and groups in which one or more carbon atoms of the aryl group are substituted with silicon or germanium atoms. R ^{8 to} R ¹⁹ may be the same as or different from each other.

Moreover, at least one set of the groups adjacent to 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, cyclohex Silidene (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, phenylmeth 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, isopropylide (3-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butylcyclopentadienyl) (octamethyloctahydridodibenzfluorene) Nyl) 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) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconi Um 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 di Loride, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclopenta) Dienyl) (octamethyloctahydridodibenzfluorenyl) 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- Butyl fluoreni ) Zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylidene (3-tert-butyl-5-methylcyclopenta) 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 Hydrido-dibenzfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5-methylcyclopenta) Dienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorene) Nyl) zirconium dichloride, phenylmethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, and dibromide compounds of the above metallocene compounds, di 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.

  Of the transition metal compounds represented by the general formulas (II), (III), and (IV), preferred compounds are those represented by the general formulas (II) and (III). It is a transition metal compound represented by the formula (II). Among the transition metal compounds represented by the general formula (II), ethylene bis (indenyl) zirconium dichloride and dimethylsilylene bis (indenyl) zirconium dichloride are particularly preferable.

  The (B) organoaluminum oxy compound (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. It may be a benzene insoluble organoaluminum oxy compound.

Conventionally known alumoxanes can be produced, for example, by the following methods (1) to (3).
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to and reacted with a suspension of the above hydrocarbon medium.
(2) A method of allowing water, ice or water vapor 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 organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

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

  Specific examples of organoaluminum compounds used in the preparation of alumoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tris-butylaluminum, trialuminum. Trialkylaluminum such as t-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum and tridecylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diethyl Dialkyl such as aluminum bromide, 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, trialkylaluminum and tricycloalkylaluminum are particularly preferable. Moreover, the isoprenyl aluminum represented by the following general formula (VI) can also be used as the organoaluminum compound used when preparing the alumoxane.

_{(I-C 4 H 9)} x Al y (C 5 H 10) z ... (VI)
(In the formula, x, y, and z are positive numbers, and z ≧ 2x.)
The above organoaluminum compounds are used alone or in combination.

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

  Further, the benzene-insoluble organoaluminum oxy compound that can be used in the present invention is a method of bringing a solution of alumoxane into contact with water or an active hydrogen-containing compound, or a method of bringing the organoaluminum compound into contact with water as described above. Can be obtained by: Such a benzene-insoluble organoaluminum oxy compound has an Al component dissolved 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 organoaluminum oxy compound (B) as described above is usually marketed or handled as a toluene solution. The organoaluminum oxy compound (B) used in the present invention may contain a small amount of a metal organic compound component other than aluminum.

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

[In the formula (I), R is an (o + p) -valent group containing one or more halogen atoms, 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 to} C ₂₀ hydrocarbon group, a C _{1 to} C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, or a sulfur-containing group. , An arbitrary group selected from 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. ]

In 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.
Examples of the C _{1 to} C ₂₀ hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-hexyl group, and an n-decyl group. Alkyl groups, phenyl groups, 1-naphthyl groups, aryl groups such as 2-naphthyl groups, and aralkyl groups such as benzyl groups.

Examples of the C _{1 to} C ₂₀ halogen-containing hydrocarbon group include groups in which one or more hydrogen atoms in the hydrocarbon group are substituted with an appropriate halogen atom, such as a trifluoromethyl group. Examples of the silicon-containing group include a trimethylsilyl group and dimethyl (t-butyl) silyl group. 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. 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 polyfunctional organic halides represented by the above general formula (I) include OH—R—OH type compounds (the definition of R is the same as that of the general formula (I)), and 3-fluoro 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 (trifluorome 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) resorcin, 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) hydride Rhoquinone, 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-propaneglycol, 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 above OH-R- The compound etc. which substituted the fluorine atom of OH compound by the bromine atom and the chlorine atom are mentioned.

As the H ₂ N—R—NH ₂ compound (the definition of R is the same as that of the general formula (I)), 2-amino-3-fluoroaniline, 2-amino-4-fluoroaniline, 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, 4 -Amino-2-fluoroaniline, 4-amino-3-fluoroaniline, 4-amino-2,3-difluoroaniline, 4-amino-2,5-difluoroaniline 4-amino-2,6-difluoroaniline, 4-amino-2,3,5-trifluoroaniline, 4-amino-2,3,6-trifluoroaniline, 4-amino-tetrafluoroaniline, 4 -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, tetrafluoroethylene di Min, hexafluoro-1,3-propenediamine, 2,2 ′, 3,3′-tetrafluoro-1,4-butylenediamine, octafluoro-1,4-butylenediamine, decafluoro-1,5-pentene Fluorine atoms of diamine, perfluoro-1,6-hexenediamine, perfluoro-1,7-heptenediamine, perfluoro-1,8-octenediamine and the above H ₂ N—R—NH ₂ compound were substituted with bromine atoms and chlorine atoms. Compounds and the like.

  HLN-R-NLH type compounds (the definitions of R and L are the same as those in 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-phenyl 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 -Di ( 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 , 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 include methylxanthine, 3-fluoromethyladenine, and compounds in which the fluorine atom of the HLN-R-NLH type compound is substituted with a bromine atom or a chlorine atom.

HO—R—NH type ₂ compounds (the definition of R is the same as in 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-tri 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) fluoro Nord, 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 (tri 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-trifluoro (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-hydroxynaphthalene naphthalene, 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-arboxamidooxime, 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.

  HO-R-NLH type compounds (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, 3 -(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-trifluoro 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-methylaphthalene) C) -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 Oro 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-phenyl 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-trif 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-trifluoro) 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 Rho 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-trif Examples thereof include compounds in which the fluorine atom of (olomethylamino) perfluoro-1-heptanol, 8- (N-trifluoromethylamino) perfluoro-1-octanol and the above HO-R-NLH type compound is substituted with a bromine atom or a chlorine atom. .

H ₂ N—R—NLH type compounds (the definitions of L and R are the same as those in formula (I)) include 2- (N-methylamino) -3-fluoroaniline, 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 C) -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) Naphthalenenaphthalene, 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- Tilamino) 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 Rophenyl) 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-fluorofailhydrazine, 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 include phenylhydrazine, 2-amino-6-fluoro-purine, 2-amino-6-trifluoromethyl-purine, and compounds in which the fluorine atom of the H ₂ N—R—NLH type compound is substituted with a bromine atom or a chlorine atom. .

  Of these, 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, 4-amino-3-fluorophenol, particularly preferably tetrafluororesorcin, tetrafluorohydroquinone, tetrabromohydroquinone, 4,4′-diaminooctafluorobiphenyl, 2,2 ′ , 3,3′-tetrafluoro-1,4-butanediol, and particularly preferred is tetrafluorohydroquinone.

  Examples of the (D) organoaluminum compound (hereinafter sometimes referred to as “component (D)”) used in the present invention include an organoaluminum compound represented by the following general formula (VII). .

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), R ^a is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group. Specifically, a methyl group, an ethyl group, an n-propyl group, Examples thereof include isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, isohexyl group, heptyl group, nonyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

  Specific examples of the organoaluminum compound (d) include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; isoprenylaluminum Alkenyl aluminum: Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide; methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum SE Alkylaluminum sesquihalides such as kibromide; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide; dimethylaluminum hydride, diethylaluminum hydride, dihydrophenylaluminum, diisopropylaluminum 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 It is.

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

^{_{R a n AlU 3-n ...}} (VIII)
(In the formula, R ^a is the same as above, and U represents —OR ^b group, —OSiR ^c ₃ group, —OAlR ^d ₂ group, —NR ^e ₂ group, —SiR ^f ₃ group, or —N (R ^g ). AlR ^h ₂ group, n is 1-2, R ^b , R ^c , R ^d , and R ^h are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group, etc. ^e is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc., and R ^f and R ^g are a methyl group, an ethyl group, etc.

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 ) _3-n , for example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) _2, etc .; (4) R ^a _n Al (NR ^e ) _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 ] _3-n compounds such as Et ₂ AlN (Me) AlEt ₂ , (iso-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

Among the organoaluminum compounds represented by the above general formulas (VII) and (VIII), compounds represented by the general formula R ^a ₃ Al are preferable, and R ^a is an alkyl group having 1 to 4 carbon atoms Is preferred.

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 1 to 300 μm, preferably 3 to 200 μm is used. Of these, porous oxides are preferable as the inorganic carrier, and specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, etc., or these 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, etc. be able to. Among these, 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. The inorganic oxide includes 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 , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

Such a solid carrier has different properties depending on the type and 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. The pore volume is desirably 0.3 to 2.5 cm ³ / g. The solid carrier is used after calcining at a temperature of 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

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

  The olefin polymerization catalyst according to the present invention is necessary after contact treatment of an inert hydrocarbon solution in which both the component (A) and the component (B) are dissolved in a suspension solution containing the solid carrier and the component (B). The organic aluminum oxy compound (B) or the organoaluminum compound (D) is further brought into contact with each other.

  Next, the solid catalyst for olefin polymerization of the present invention will be described more specifically. The first solid catalyst for olefin polymerization according to the present invention is a periodic table 4 containing one or more ligands having a cyclopentadienyl skeleton in a suspension containing a solid support and an organoaluminum oxy compound (B). It is characterized by being obtained by contacting an inert hydrocarbon solution in which the group III transition metal compound (A) and the polyfunctional organic halide (C) are dissolved together.

  The above-mentioned catalyst for olefin polymerization is a suspension using an inactivated hydrocarbon solvent containing a solid carrier and component (B) obtained by contacting the solid carrier with component (B) in an inert hydrocarbon solvent. It can be prepared by bringing the liquid into contact with an inert hydrocarbon solution in which component (A) and component (C) are mixed and dissolved.

  The second olefin polymerization catalyst according to the present invention includes a suspension containing a solid carrier and an organoaluminum oxy compound (B), which is a group of Periodic Table 4 containing at least one ligand having a cyclopentadienyl skeleton. After an inert hydrocarbon solution in which the transition metal compound (A) and the polyfunctional organic halide (C) are dissolved together is contact-treated, at least one selected from the organoaluminum oxy compound (B) or the organoaluminum compound (D) It is characterized by being obtained by further contacting two or more compounds.

  The above-mentioned catalyst for olefin polymerization is a suspension using an inactivated hydrocarbon solvent containing a solid carrier and component (B) obtained by contacting the solid carrier with component (B) in an inert hydrocarbon solvent. The liquid is contacted with an inert hydrocarbon solution in which component (A) and component (C) are mixed and dissolved, and then further contacted with at least one compound selected from component (B) or component (D) Can be prepared.

In the present invention, the mixing and contacting the above components, the solid carrier and component (B), the solid carrier 1g per component ^(B), 10 -5 to 10 ^-1 mol, preferably 5 × 10 ^- Used in an amount of ^{5 to} 5 × 10 ⁻² mol and the contact concentration of component (B) is in the range of 10 ^{−1 to} 20 mol / liter-solvent, preferably 5 × 10 ⁻¹ to 10 mol / liter-solvent. It is. Component (A) is an atomic ratio (Al / transition metal) between aluminum (Al) derived from component (B) and a transition metal derived from component (A), and is 10 to 1000, preferably 50 to 500. Used in the amount of. Component (C) is 0.01 to 5.0 mol, preferably 0.02 to 1.0 mol, more preferably 0.03 to 0.5 mol, relative to 1 mol of aluminum derived from component (B). Used in the amount of. When component (D) is used, the gram atomic ratio (Al-D / A) of aluminum atom (Al-D) in component (D) to aluminum atom (Al-b) in component (b) is used. Al-B) and is used in an amount of 0.01 to 2.0, preferably 0.02 to 1.0.

The mixing temperature at the time of mixing each of 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.
Specific examples of the inert hydrocarbon solvent used for preparing the catalyst in the present invention include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methyl Examples thereof include alicyclic hydrocarbons such as cyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof.
In the (co) polymerization of ethylene, the olefin polymerization catalyst as described above can be used as it is, but the olefin polymerization catalyst can be prepolymerized to form a prepolymerization catalyst.
The prepolymerization catalyst can be prepared by prepolymerizing an olefin usually in an inert hydrocarbon solvent in the presence of the olefin polymerization catalyst. In addition to this olefin polymerization catalyst, component (D) may be further added.

Concentration in the preliminary polymerization system in the olefin polymerization catalyst, the transition metal / polymerization volume 1 liter ratio, usually ¹⁰ -6 ^~2 × ^{10 -1} mol / liter, more 5 × ¹⁰ -5 ~10 ^-1 mol / It is desirable to be liters.

The prepolymerization temperature is -20 to 90 ° C, preferably 0 to 80 ° C, and the prepolymerization time is 0.05 to 100 hours, preferably about 0.5 to 80 hours. In the prepolymerization, an olefin similar to the olefin used in the polymerization described later is used, but an olefin mainly composed of ethylene is preferable.
The prepolymerization catalyst may introduce olefin into an olefin polymerization catalyst suspension prepared using an inert hydrocarbon solvent, and the olefin polymerization catalyst produced in the inert hydrocarbon solvent is separated from the suspension. After that, it 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 olefin polymerization catalyst. .

The prepolymerization can be carried out in any of batch, semi-continuous and continuous methods. In the prepolymerized catalyst thus obtained, the transition metal atom derived from the component (A) is 10 ⁻⁷ to 4 × 10 ⁻² gram atom, preferably 5 × 10 ⁻⁷ to 2 ×, per 1 g of the solid support. ^10-2 gram amount of atoms in the supported, aluminum atoms ¹⁰ -6 to 9.0 × ^{10 -1} gram atom derived from the component (B), preferably 5 × ¹⁰ -6 ~5 × ^{10 -1} gram atom The component (C) is preferably supported in an amount of 5 × 10 ⁻⁸ to 4 × 10 ⁻² mol, preferably 10 ⁻⁸ to 2 × 10 ⁻² mol.

  The prepolymerization can be performed either batchwise or continuously, and can be performed under reduced pressure, normal pressure, or increased pressure.

  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 above solid catalyst for olefin polymerization. The polymerization can be carried out by any of liquid phase polymerization methods such as suspension polymerization or gas phase polymerization methods.

In the liquid phase polymerization method, the same inert hydrocarbon used in the catalyst preparation described above can be used as the solvent, or the olefin itself can be used as the solvent.
When performing olefin polymerization using the olefin polymerization catalyst of the present invention, the catalyst as described above is 10 ⁻⁸ to 10 ⁻³ gram as the concentration of transition metal atoms derived from the component (A) in the polymerization system. It is desirable to use in an amount of atoms / liter (polymerization volume), preferably 10 ⁻⁷ to 10 ⁻⁴ grams atom / liter (polymerization volume). At this time, an organoaluminum oxy compound may be used if desired. The amount of the organoaluminum 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 polymerization temperature of the olefin is desirably in the range of −50 to 100 ° C., preferably 0 to 90 ° C. when the slurry polymerization method is performed, and 0 to 250 when the liquid phase polymerization method is performed. It is desirable that the temperature be in the range of 20 ° C to 200 ° C. When carrying out the gas phase polymerization method, the polymerization temperature is 0 to 120 ° C, preferably 20 to 100 ° C. The polymerization pressure is under normal pressure to 10 MPa, preferably normal pressure to 5 MPa, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, 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 allowing hydrogen to be present in the polymerization system or changing the polymerization temperature. Examples of the olefin that can be polymerized by the olefin polymerization catalyst of the present invention include ethylene and an α-olefin having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 4- Methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; cyclic olefins having 5 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene , 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, etc. Can do. Furthermore, styrene, vinylcyclohexane, diene, etc. can also be used.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

  The polymer weight average molecular weight (Mw) and Z average molecular weight (Mz) were measured as follows.

The weight average molecular weight (Mw) and the Z average molecular weight (Mz) were calculated from a molecular weight distribution curve 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 measurement equipment; gel permeation chromatograph allianceGPC2000 (Waters)
Analysis software: Chromatography data system Empower (Waters)
Column: TSKgel GMH ₆ -HT x 2 + TSKgel GMH _6- HTL x 2
(Inner diameter 7.5mm x length 30cm, 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 Monodispersed polystyrene (Tosoh Corp.) / Molecular weight 495 to molecular weight 20.6 million Molecular weight distribution and various average molecular weights were calculated as PE molecular weight conversion according to the general calibration procedure described in Reference 1).
1) Z. Crubisic, P. Rempp, H. Benoit, J. Polym. Sci., B5 , 753 (1967)

Preparation of solid component (S1) 13 g of silica (SiO ₂ ) dried at 250 ° C. for 10 hours under nitrogen flow was suspended in 100 mL of toluene, and then cooled to 0 ° C. To this suspension, 52.6 mL of a toluene solution of methylalumoxane (component B: Albemarle product) (1.75 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. The solid component thus obtained was washed four times with toluene, and then toluene was added to prepare a toluene slurry of the solid component (S1). A part of the obtained solid component (S1) was collected and examined for concentration. As a result, the slurry concentration was 0.1699 g / mL and the Al concentration was 0.804 mmol / mL.

Preparation of solid catalyst component (X-1) To a nitrogen-substituted 200 mL glass flask was charged 50 mL of toluene, and with stirring, the toluene slurry of the solid component (S1) prepared above (2.0 g in terms of solid part) was loaded. The temperature was raised to 80 ° C. Next, 31.6 ml of a separately prepared toluene solution of ethylenebis (indenyl) zirconium dichloride (component A) (0.0015 mmol / mL in terms of Zr atom) and a toluene solution of tetrafluorohydroquinone (component C) (0.05 mmol / ml) A 19.0 ml mixed solution (total amount 50.6 ml) was slowly added dropwise over 10 minutes. The reaction was performed at 80 ° C. for 60 minutes. After completion of the reaction, the supernatant was removed by decantation, washed once with toluene, then twice with decane, and 100 mL of decane was added to prepare a decane slurry of the solid catalyst component (X-1). When a part of the resulting decane slurry of the solid catalyst component (X-1) was collected to examine the concentration, the Zr concentration was 0.0294 mg / mL and the Al concentration was 2.16 mg / mL.

Polymerization Purified heptane (500 mL) was placed in a 1-liter SUS autoclave sufficiently purged with nitrogen, ethylene was circulated, and the liquid phase and gas phase were saturated with ethylene. In an ethylene atmosphere at 20 ° C., 0.375 mmol of triisobutylaluminum and solid catalyst component (X-1) (0.002 mmol in terms of zirconium atom) were charged in this order. Polymerization was carried out at 20 ° C. for 2 hours with an ethylene pressure of 0.78 MPa · G. The obtained polymer was vacuum-dried for 10 hours to obtain 0.78 g of an ethylene polymer. When the obtained polymer was subjected to gel permeation chromatography measurement (GPC), Mw of the polymer was 187.5 × 10 ⁴ and Mz was 744.2 × 10 ⁴ .

Preparation of solid catalyst component (X-2) 50 mL of toluene was placed in a 200 mL glass flask substituted with nitrogen, and the toluene slurry of the solid component (S1) prepared above (2.0 g in terms of solid part) was charged with stirring. The temperature was raised to 80 ° C. Next, 31.6 ml of a separately prepared toluene solution of ethylenebis (indenyl) zirconium dichloride (component A) (0.0015 mmol / mL in terms of Zr atom) and a toluene solution of tetrafluorohydroquinone (component C) (0.05 mmol / ml) 38.0 ml of a mixed solution (total amount 69.6 ml) was slowly added dropwise over 10 minutes. The reaction was performed at 80 ° C. for 60 minutes. Thereafter, the supernatant was removed by decantation and washed once with toluene to give a 50 mL toluene slurry. Furthermore, after heating up to 80 degreeC, 36.2 mL of toluene solutions (0.422 mmol / mL in conversion of Al atom) of methylalumoxane (albemarle product; component B) are dripped over 10 minutes, 30 degreeC is 30 degreeC. Reacted for 1 minute. Thereafter, the supernatant was removed by decantation, washed twice with toluene and twice with decane, and 100 mL of decane was added to prepare a decane slurry of the solid catalyst component (X-2). A part of the resulting decane slurry of the solid catalyst component (X-2) was collected to examine the concentration. As a result, the Zr concentration was 0.034 mg / mL and the Al concentration was 4.67 mg / mL.

In the polymerization example 1, it carried out like Example 1 except having used the solid catalyst component (X-2) instead of the solid catalyst component (X-1). The obtained polymer was vacuum-dried for 10 hours to obtain 1.1 g of an ethylene polymer. When the obtained polymer was subjected to gel permeation chromatography measurement (GPC), Mw of the polymer was 143.7 × 10 ⁴ and Mz was 665.9 × 10 ⁴ .

[Comparative Example 1]
Preparation of solid catalyst component (X-3)
50 mL of toluene was placed in a 200 mL glass flask purged with nitrogen, and the toluene slurry of the solid component (S1) prepared above (2.0 g in terms of solid part) was charged with stirring, and the temperature was raised to 80 ° C. Next, 31.6 ml of a toluene solution of ethylenebis (indenyl) zirconium dichloride (component A) (0.0015 mmol / mL in terms of Zr atoms) was slowly added dropwise over 10 minutes and reacted at 80 ° C. for 60 minutes. Thereafter, the supernatant was removed by decantation, washed twice with toluene and twice with decane, and 100 mL of decane was added to prepare a decane slurry of the solid catalyst component (X-3). A part of the resulting decane slurry of the solid catalyst component (X-3) was collected to examine the concentration. As a result, the Zr concentration was 0.0334 mg / mL and the Al concentration was 2.25 mg / mL.

In the polymerization example 1, it carried out like Example 1 except having used the solid catalyst component (X-3) instead of the solid catalyst component (X-1). The obtained polymer was vacuum-dried for 10 hours to obtain 1.8 g of an ethylene polymer. When the obtained polymer was subjected to gel permeation chromatography measurement (GPC), Mw of the polymer was 50.6 × 10 ⁴ and Mz was 391.2 × 10 ⁴ .

Claims (6)

  Group 4 transition metal compound (A) and polyfunctional organic halogen containing at least one ligand having a cyclopentadienyl skeleton in a suspension containing a solid support and an organoaluminum oxy compound (B) A catalyst for olefin polymerization obtained by contacting an inert hydrocarbon solution in which the chemical compound (C) is dissolved together.   Group 4 transition metal compound (A) and polyfunctional organic halogen containing at least one ligand having a cyclopentadienyl skeleton in a suspension containing a solid support and an organoaluminum oxy compound (B) An olefin obtained by contacting an inert hydrocarbon solution in which the compound (C) is dissolved together, and then further contacting at least one compound selected from the organoaluminum oxy compound (B) and the organoaluminum compound (D) Polymerization catalyst. The olefin polymerization catalyst according to claim 1 or 2, 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 one or more halogen atoms, 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 to} C ₂₀ hydrocarbon group, a C _{1 to} C ₂₀ halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, or a sulfur-containing group. , An arbitrary group selected from a nitrogen-containing group or a phosphorus-containing group), and L and R, N and R, and N and N may be bonded to each other to form a ring. ]   4. The olefin polymerization catalyst according to claim 1, wherein the polyfunctional organic halide (C) is tetrafluorohydroquinone. 5. An olefin polymer is produced in the presence of the olefin polymerization catalyst according to any one of claims 1 to 4, wherein the olefin polymer is produced.   The method for producing an olefin polymer according to claim 5, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.