JP4889919B2 - Solid catalyst for olefin polymerization and olefin polymerization method using the same - Google Patents

Description

  The present invention relates to an olefin polymerization catalyst and an olefin polymerization method using the catalyst, and more specifically, an olefin polymerization catalyst that provides a high activity olefin polymer having high melt tension and excellent mechanical strength, and the olefin polymerization catalyst. The present invention relates to an olefin polymerization method using a catalyst.

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

  In addition, as a catalyst capable of producing an ethylene / olefin copolymer with high polymerization activity, an olefin polymerization catalyst (metallocene catalyst) composed of a zirconium compound and an organoaluminum oxy compound (alumoxane) is known. Examples of a method for producing an ethylene / olefin copolymer using a catalyst include, for example, JP-A-58-19309, JP-A-60-35005, JP-A-60-35006, and JP-A-60-35007. Japanese Laid-Open Patent Publication No. 60-35008 and so on.

  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.

  However, in any of the ethylene polymer or ethylene-olefin copolymer produced using the catalyst as described above, since the melt tension and the melt viscoelasticity are insufficient, for example, the valve shakes at the time of forming an inflation film, Alternatively, there was a limit to high-speed molding in a stable state without tearing. Also, in hollow molding that requires similar characteristics, phenomena such as sagging or tearing tend to occur. Furthermore, when trying to form a cast film in the T-die molding, there is a problem that a neck-in occurs in which the film end portion shrinks toward the center. When neck-in occurs, the film width decreases and the thickness of the film end increases compared to the center of the film, resulting in poor product yield.

  By the way, many methods for improving the moldability by improving the melt tension and expansion ratio (die swell ratio) of an ethylene polymer have been proposed. For example, a method using a Ziegler type titanium catalyst is disclosed in Japanese Patent Laid-Open No. 56-90810 or Japanese Patent Laid-Open No. 60-106806. Among ethylene polymers produced using Ziegler-type catalysts, ethylene polymers obtained using chromium-based catalysts are relatively inferior in thermal stability but have relatively high melt tension. This is presumably because the chain end of the ethylene polymer produced using a chromium-based catalyst tends to become an unsaturated bond. However, ethylene polymers obtained using a titanium-based catalyst or chromium-based catalyst, particularly low-density ethylene-based copolymers, have a wide composition distribution, and molded articles such as films have problems such as stickiness. It was.

  On the other hand, an ethylene polymer obtained using a metallocene catalyst has a low melt tension, but is excellent in mechanical strength such as tensile strength, tear strength or impact strength, has a narrow composition distribution, and a molded product such as a film is sticky. It is known that there are advantages such as less. Examples of methods for improving the melt tension utilizing the advantages of the metallocene catalyst include, for example, JP-A-4-213306 (a method of copolymerizing ethylene and an α-olefin such as 1-butene) and JP-A-1-50163. Japanese Laid-Open Patent Publication No. 4-506372 (Method of copolymerizing ethylene and 1,3-butadiene) and Japanese Patent Publication No. 4-506372 (Method of copolymerizing ethylene and 1,4-hexadiene). However, in these methods, when a small amount of a comonomer branch or a crosslinked structure is introduced, the melting characteristics are not sufficiently improved. In addition, if introduced in a large amount, the inherent mechanical properties of the polymer may be deteriorated, or gel may be generated.

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

In order to solve this problem, a composition of a high-pressure low-density polyethylene having a high melt tension and an ethylene polymer having excellent mechanical strength obtained by using a metallocene catalyst is disclosed in, for example, WO99 / 46325. Proposed. However, in order to prepare the composition, it is necessary to perform melt blending, and a significant cost increase due to this blending is inevitable.
JP 58-19309 A JP-A-60-35005 JP-A-60-35006 Japanese Unexamined Patent Publication No. 60-35007 JP 60-35008 A JP 60-260602 A JP 60-130604 A JP 56-90810 A JP 60-106806 A JP-A-4-213306 Japanese National Publication No. 1-50163 JP-T-4-506372 WO99 / 46325 publication

  As described above, it has been difficult to obtain a resin having a high melt tension and excellent mechanical strength at low cost and efficiently with a conventionally known catalyst system or resin blending technique. In other words, the emergence of an efficient production technique for an ethylene polymer having both high melt tension and excellent mechanical strength is important for industrial production and its value is extremely high.

  The present invention has been made in view of the situation as described above, and provides an olefin polymerization catalyst in which an olefin polymer having high melt tension and excellent mechanical strength can be obtained with high activity. The object is to provide an olefin polymerization method using the olefin polymerization catalyst.

  As a result of diligent research in view of such circumstances, the present inventors have found that the transition metal of Group 4 of the periodic table contains a solid carrier and (A) (a) one or more ligands having a cyclopentadienyl skeleton. A compound, (b) an organoaluminum oxy compound, and (c) a polyfunctional organic halide 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. ], A solid transition metal catalyst component obtained by contacting with a solid catalyst for olefin polymerization formed from (B) an organoaluminum compound, if necessary, has a high melt tension and excellent mechanical strength. The inventors have found that an olefin polymer can be polymerized with high activity and have completed the present invention.

  That is, the first olefin polymerization catalyst according to the present invention is a transition metal compound of Group 4 of the periodic table containing a solid support and (A) (a) one or more ligands having a cyclopentadienyl skeleton, b) an organoaluminum oxy compound, and (c) a solid transition metal catalyst component obtained by contacting a polyfunctional organic halide represented by the general formula (I), and (B) an organoaluminum compound as required. It is characterized by consisting of.

[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. ]
Moreover, the 2nd olefin polymerization catalyst which concerns on this invention is a transition metal compound of the periodic table group 4 containing the solid support | carrier and (A) (a) one or more ligands which have a cyclopentadienyl skeleton, ( b) an organoaluminum oxy compound, (c) a polyfunctional organic halide represented by the general formula (I), and (d) a solid transition metal catalyst component obtained by contacting the organoaluminum compound, and if necessary (B) It consists of an organoaluminum compound.

    The transition metal compound belonging to Group 4 of the periodic table containing at least one ligand having a cyclopentadienyl skeleton 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 ^{10 to} R ²⁰ 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 aryl or C ₇ -C arylalkyl group ₂₀ silicon, may comprise a halogen or germanium atom, adjacent substituents to R ⁸ to R ¹⁹ 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. ]
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 an olefin polymerization catalyst and a method for producing an olefin polymer, an olefin polymer having a high melt tension and excellent mechanical strength can be obtained with high activity.

  The olefin polymerization catalyst according to the present invention can produce an olefin polymer having high melt tension and excellent mechanical strength 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 described in detail. 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 (a) 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 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 components (a-1), (a-2) and (a At least one component selected from -3) is preferably used.

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

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 (I) and (II) 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 as 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).

  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 hydrocarbon in
(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.

  (C) used in the present invention (hereinafter sometimes referred to as “component (c)”) is a polyfunctional organic halide 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 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- Fluorocatechol, 4-fluorocatechol, 3,4-difluorocatechol, 3,5-difluorocatechol, 3,6-difluorocatechol, 3,4,5-trifluorocatechol, 3,4,6-trifluorocatechol, tetra Fluorocatechol, 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 (trifluoro) Til) 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, , 6-di (trifluoromethyl) resorcin, 2,4,5-tri (trifluoromethyl) resorcin, 4,5,6-tri (trifluoromethyl) resorcin, tetra (trifluoromethyl) resorcin, 2-fluoro Hydroquinone, 3-fluorohydroquinone, 2,3-difluorohydroquinone, 2,5-difluorohydroquinone, 2,6-difluorohydroquinone, 2,3,5-trifluorohydroquinone, 2,3,6-trifluorohydroquinone, tetrafluoro Hydroquinone, 2- (trifluoromethyl) hydroquinone, 3- (trifluoromethyl) hydroquinone, 2,3-di (trifluoromethyl) hydroquinone, 2,5-di (trifluoromethyl) hydroquinone, 2,6-di ( Trifluoromethyl) high Droquinone, 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, -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, , 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'-tetra Fluoro-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-butanedio , 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 the -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) benzamidoxime, 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.

Examples of the (a) 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 ^Rf and ^Rg 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.

In the olefin polymerization catalyst according to the present invention, the above-described components are supported on a solid carrier as described below. 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.

  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 transition metal compound of Group 4 of the periodic table comprising a solid support and (A) (a) one or more ligands having a cyclopentadienyl skeleton, a solid transition metal catalyst component obtained by contacting b) an organoaluminum oxy compound, and (c) a polyfunctional organic halide represented by the general formula (I), and (B) an organoaluminum compound. It is a feature.

[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, 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. ]
The solid transition metal catalyst component (A) can be prepared by mixing and contacting the component (a), the component (b), the component (c) and the solid support in an inert hydrocarbon.

  The order of mixing the components at this time is arbitrary, but it is desirable to avoid mixing and contacting the component (a) and the component (c) directly. Such direct contact may cause decomposition and alteration of the component (a), and there is a high possibility that the catalytic activity of the finally obtained olefin polymerization catalyst will be significantly reduced.

As a preferable contact order, for example,
i) A method in which component (b) is mixed and contacted with a solid carrier, and then component (a) is contacted and then component (c) is contacted.
ii) A method in which component (b) is mixed and contacted with a solid carrier, and then component (c) is contacted, and then component (a) is contacted,
iii) A method in which component (a) and component (b) are first mixed and contacted, and then a solid carrier and subsequently component (c) are mixed and contacted,
iv) A method in which a solid carrier is brought into contact with the contact mixture of component (b) and component (c), and then component (a) is mixed and contacted
v) A method wherein the component (b) is mixed and contacted with the solid carrier, then the component (a) is contacted, the component (c) is contacted, and the component (b) is contacted again.
vi) A method in which component (b) is mixed and contacted with a solid carrier, then component (c) is contacted, component (b) is contacted again, and component (a) is further contacted.
vii) A method in which the component (a) and the component (b) are first mixed and contacted, then the solid carrier, then the component (c), and the component (b) is again mixed and contacted.

  The second olefin polymerization catalyst according to the present invention is a transition metal compound of Group 4 of the periodic table containing a solid carrier and (A) (a) one or more ligands having a cyclopentadienyl skeleton, (b) An organoaluminum oxy compound, (c) a polyfunctional organic halide represented by general formula (I), and (d) a solid transition metal catalyst component obtained by contacting an organoaluminum compound, and (B) organoaluminum It consists of a compound.

  The solid transition metal catalyst component (A) is prepared by mixing and contacting the component (a), the component (b), the component (c), the component (d) and the solid support in an inert hydrocarbon. be able to.

  The order of mixing the components at this time is arbitrary, but it is desirable to avoid mixing and contacting the component (a) and the component (c) for the same reason as described above.

As a preferable contact order, for example,
i) The component (b) is mixed and contacted with the solid carrier, and then the component (a) is contacted, and then the component (c), the component (d), or the contact between the component (c) and the component (d) A method of contacting the mixture,
ii) After contacting component (b) with the solid carrier and then contacting component (c),
A method of contacting component (a) or component (d);
iii) First, the component (a) and the component (b) are mixed and contacted, and then the solid carrier, followed by the component (c), the component (d), or the contact mixture of the component (c) and the component (d), How to contact,
iv) A method in which a solid carrier is brought into contact with the contact mixture of component (b) and component (c) and then component (a) or component (d) is mixed and contacted.

Examples of the (B) organoaluminum compound (hereinafter sometimes referred to as “component (B)”) used as necessary in the present invention include the same organoaluminum compounds as the component (d), among the general formula _{^{R a 3 Al, R a n}} Al (OR b) 3-n, can be cited as a preferred example organoaluminum compounds represented by _{^{R a n Al (OAlR d 2}} ) 3-n A compound in which R ^a is an isoalkyl group and n = 2 is particularly preferable.

In the present invention, when the above components are mixed, the component (a) is 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 5 × 10 ⁻⁶ to 2 × 10 ⁻⁴ mol, per 1 g of the solid carrier. The concentration of component (a) is in the range of 10 ⁻⁵ to 10 ⁻² mol / liter-solvent, preferably 5 × 10 ^{−5 to} 5 × 10 ⁻³ mol / liter-solvent. Component (b) 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, a gram atomic ratio (Al-d / a) of aluminum atom (Al-d) in component (d) and 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.

  In the present invention, as one of the preferred contact forms, the component (b) and the component (c) are mixed and contacted in advance in an inert hydrocarbon, and include a mixed contact product of the component (b) and the component (c). After preparing the solution, there can be mentioned a method in which the solution and other components are mixed and contacted. In mixing and contacting the component (b) and the component (c), the concentration of the component (b) is in the range of 0.01 to 5 mol / liter-solvent, preferably 0.1 to 3 mol / liter-solvent. is there. 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). It is desirable that the amount of The mixing temperature at the time of mixing and contacting the component (b) and the component (c) is −90 to 150 ° C., preferably −80 ° C. to 120 ° C., and the contact time is 1 to 1000 minutes, preferably 5 to 600 minutes. It is.

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

In the first olefin polymerization catalyst according to the present invention, the transition metal atom derived from the component (a) is 10 ^{−4 to} 5 × 10 ⁻² gram atom, preferably 5.0 × 10 ⁻ , per 1 g of the solid support. Supported in an amount of ^{4 to} 2 × 10 ⁻² gram atoms, aluminum atoms derived from component (b) are 10 ^{−4 to} 1.0 gram atoms, preferably 5 × 10 ^{−3 to} 5 × 10 ⁻¹ gram atoms. It is desirable that the component (c) is supported in an amount of 5 × 10 ^{−5 to} 5 × 10 ⁻² mol, preferably 10 ⁻⁵ to 10 ⁻² mol. The component (B) used as necessary is desirably used in an amount of 500 mol or less, preferably 1 to 200 mol per gram atom of the transition metal atom derived from the component (a).

In the second olefin polymerization catalyst according to the present invention, the transition metal atom derived from the component (a). Aluminum derived from component (b) and component (d), supported in an amount of 5 × 10 ^{−5 to} 5 × 10 ⁻² gram atoms, preferably 10 ⁻⁵ to 10 ⁻² gram atoms per gram of solid support. The atoms are supported in an amount of 10 ^{−3 to} 1.0 gram atoms, preferably 5 × 10 ^{−3 to} 5 × 10 ⁻¹ gram atoms, and component (c) is 5 × 10 ^{−5 to} 5 × 10 ^−2. It is desirable that it is supported in an amount of 10 mol, preferably ^10-5 to ^10-2 mol. The component (B) used as necessary is desirably used in an amount of 500 mol or less, preferably 1 to 200 mol per gram atom of the transition metal atom derived from the component (a).
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 component (a), the component (b), the component (c) and the solid carrier. In addition, it is preferable that the olefin polymerization catalyst is formed from each said component (a), component (b), component (c), and a solid support. In addition to this olefin polymerization catalyst, component (d) may be further added.

In the preliminary polymerization, the component (a) is used in an amount of 10 ^{−6 to} 5 × 10 ⁻⁴ mol, preferably 5 × 10 ⁻⁶ to 2 × 10 ⁻⁴ mol as a transition metal per 1 g of the solid support. Component (b) is an atomic ratio (Al / transition metal) of aluminum (Al) of component (b) and transition metal of component (a), and is used in an amount of 10 to 1000, preferably 50 to 500. . Component (c) is used in an amount of 0.01 to 5.0 mol, preferably 0.02 to 1.0 mol, more preferably 0.03 to 0.5 mol, per 1 mol of component (b). It is done. When component (d) is used, the atomic ratio (Al-d / Al) of aluminum atoms (Al-d) in component (d) to aluminum atoms (Al-b) in component (b) -B) is used in an amount of 0.01 to 5.0, preferably 0.02 to 1.0.

The concentration of the transition metal compound (a) or the olefin polymerization catalyst formed from each component in the prepolymerization system is usually 10 ⁻⁶ to 2 × 10 ⁻¹ mol / liter in a transition metal / polymerization volume ratio of 1 liter, 5 × 10 ⁻⁵ to 10 ⁻¹ mol / liter is desirable.

The prepolymerization temperature is -20 to 90 ° C, preferably 0 to 80 ° C, and the prepolymerization time is 0.5 to 100 hours, preferably about 1 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.

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

The 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. Supported in an amount of 10 ⁻² gram atoms, aluminum atoms derived from component (b) are 10 ^{−6 to} 9.0 × 10 ⁻¹ gram atoms, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻¹ gram atoms. It is desirable that the component (c) is 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 either a liquid phase polymerization method such as suspension polymerization or a gas phase polymerization method.

In the liquid phase polymerization method, the same inert hydrocarbon 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., preferably 20 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 melt tension (MT), melt flow rate (MFR), and density were measured by the following methods.
[Melt tension (MT)]
MT is determined by measuring the stress when a molten polymer is stretched at a constant rate. That is, using a MT tester manufactured by Toyo Seiki Seisakusho, the conditions were a resin temperature of 190 ° C., extrusion speed of 10 mm / min, winding speed of 10 to 20 m / min, nozzle diameter of 2.09 mmφ, and nozzle length of 8 mm. When measuring the melt tension, 0.1% by weight of 2,6-t-butylparacresol as a crosslinking stabilizer was previously added to the ethylene diameter polymer.
[Melt flow rate (MFR)]
It is a numerical value measured under a load of 2.16 kg at 190 ° C. according to the standard method of ASTM D-1238.
[density]
Measured by density gradient tube method.

Preparation of solid component (S1 ) 30 g of silica (SiO ₂ ) dried at 250 ° C. for 10 hours under nitrogen flow
After suspending in 0 mL of toluene, it was cooled to 0 ° C. To this suspension, 140 mL of a toluene solution of methylalumoxane [component (b)] (1.52 mmol / mL in terms of Al atom) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 to 2 ° C. Subsequently, the mixture was reacted at 0 ° C. for 30 minutes, then heated to 95 ° C. over 1.5 hours, and reacted at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by decantation. The solid component thus obtained was washed three 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 0.184 g / mL and the Al concentration was 0.889 mmol / mL.

Preparation of solid catalyst component (X-1) 100 mL of toluene was put into a 200 mL glass flask substituted with nitrogen, and a toluene slurry of solid component (S1) (2.0 g in terms of solid part) was charged with stirring. Next, 32.6 mL of a toluene solution (0.001525 mmol / mL in terms of Zr atom) of ethylenebis (indenyl) zirconium dichloride [component (a)] was added dropwise and reacted at room temperature for 2 hours. Thereafter, the supernatant was removed by decantation and washed three times with toluene to obtain 100 mL of toluene slurry. Next, 363.1 mg [component (c)] of tetrafluorohydroquinone was charged at room temperature, and the temperature was raised to 40 ° C., followed by reaction for 30 minutes. Thereafter, the supernatant was removed by decantation and washed three times with toluene to obtain 100 mL of toluene slurry. Furthermore, 50 mL of a toluene solution of methylalumoxane (albemarle product [component (b)]) (0.199 mmol / mL in terms of Al atom) was added dropwise over 10 minutes, and the temperature was raised to 40 ° C., followed by reaction for 30 minutes. I let you. Thereafter, the supernatant was removed by decantation, washed 3 times with toluene and 3 times with decane, and 100 mL of decane was added to prepare a decane slurry of the solid catalyst component (X-1). A part of the resulting decane slurry of the solid catalyst component (X-1) was collected to examine the concentration. As a result, the Zr concentration was 0.0491 mg / mL and the Al concentration was 4.89 mg / mL.

Was charged with purified heptane 500mL in Polymerization thoroughly purged with nitrogen 1-liter SUS autoclave, in the system was replaced with ethylene. Next, after replacing the inside of the system using a hydrogen-ethylene mixed gas (hydrogen concentration: 0.06 vol%), 10 mL of 1-hexene was added, 0.375 mmol of triisobutylaluminum, the solid catalyst component prepared above (X-1) (0.0005 mmol in terms of zirconium atom) was charged in this order.

Thereafter, a hydrogen-ethylene mixed gas was supplied until the pressure in the system reached 0.3 MPa · G, whereupon the gas supply was temporarily stopped and the temperature was raised. When the temperature in the system reached 75 ° C., polymerization was performed at 80 ° C. and 0.78 MPa · G for 90 minutes while continuously supplying a hydrogen-ethylene mixed gas. The obtained polymer was vacuum-dried for 10 hours to obtain 50.0 g of an ethylene / 1-hexene copolymer. The resulting copolymer had a density of 0.936 g / cm ³ , 190 ° C., MFR measured under a load of 2.16 kg, 1.1 g / 10 min, and a melt tension of 5.6 g.

In Polymerization Example 1, the hydrogen - ethylene mixed gas (hydrogen concentration: 0.06vol%) in place of the hydrogen - ethylene mixed gas (hydrogen concentration: 0.10vol%) in the same manner as in Example 1, except that the catalyst went. The obtained polymer was vacuum-dried for 10 hours to obtain 48.0 g of an ethylene / 1-hexene copolymer. The resulting copolymer had a density of 0.937 g / cm ³ , 190 ° C., MFR measured under a load of 2.16 kg, 2.8 g / 10 min, and a melt tension of 4.1 g.

In Polymerization Example 1, the hydrogen - ethylene mixed gas (hydrogen concentration: 0.06vol%) in place of the hydrogen - ethylene mixed gas (hydrogen concentration: 0.38vol%) in the same manner as in Example 1, except that the catalyst went. The obtained polymer was vacuum-dried for 10 hours to obtain 37.4 g of an ethylene / 1-hexene copolymer. The resulting copolymer had a density of 0.946 g / cm ³ , 190 ° C., MFR measured under a load of 2.16 kg, 14.2 g / 10 minutes, and a melt tension of 3.5 g.

In Polymerization Example 1, the hydrogen - ethylene mixed gas (hydrogen concentration: 0.06vol%) in place of the hydrogen - ethylene mixed gas (hydrogen concentration: 0.55vol%) in the same manner as in Example 1, except that the catalyst went. The obtained polymer was vacuum-dried for 10 hours to obtain 34.7 g of an ethylene / 1-hexene copolymer. The resulting copolymer had a density of 0.943 g / cm ³ , 190 ° C., MFR measured under a load of 2.16 kg, 20.1 g / 10 minutes, and a melt tension of 1.3 g.

Preparation of solid catalyst component (X-2) Toluene slurry of the solid component (S1) prepared above was added with stirring to 12.5 mL of a nitrogen-substituted 200 mL glass flask, and 3.1 g in terms of solid part) Was loaded. Next, 48.8 mL of a toluene solution (0.0015 mmol / mL in terms of Zr atom) of ethylenebis (indenyl) zirconium dichloride [component (a)] was added dropwise over 15 minutes, and the temperature was raised to 80 ° C. For 2 hours. Then, after cooling to room temperature, the supernatant was removed by decantation and washed 3 times with toluene to give a 50 mL toluene slurry. Next, this toluene slurry was cooled to -20 ° C, charged with 550.1 mg of tetrafluorohydroquinone (dissolved in 50 mL of toluene heated to 40 ° C) [component (c)], and heated to 40 ° C. Then, it was made to react for 30 minutes. Thereafter, the supernatant liquid was removed by decantation, washed with toluene three times to obtain 50 mL of toluene slurry. Further, this toluene slurry was cooled to 0 ° C., and at this temperature, 50 mL of a toluene solution of methylalumoxane [component (b)] (0.30 mmol / mL in terms of Al atom) was added dropwise over 15 minutes. After raising the temperature to 30 minutes, the reaction was allowed to proceed for 30 minutes. Thereafter, the supernatant was removed by decantation, washed 3 times with toluene and 3 times with hexane, 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 0.043 mg / mL, and the Al concentration was 4.8 mg / mL.

Was charged with purified heptane 500mL in Polymerization thoroughly purged with nitrogen 1-liter SUS autoclave, in the system was replaced with ethylene. Thereafter, 10 mL of 1-hexene, 0.375 mmol of triisobutylaluminum, and the solid catalyst component (X-2) prepared above (0.002 mmol in terms of zirconium atom) were charged in this order.

  Thereafter, ethylene was supplied until the pressure in the system reached 0.3 MPa · G, whereupon the supply of ethylene was temporarily stopped and temperature increase was started. When the temperature in the system reached 70 ° C., 300 mL of hydrogen was injected and ethylene supply was resumed. Subsequently, polymerization was carried out at 80 ° C. and 0.78 MPa · G for 1 hour while continuously supplying ethylene.

After completion of the polymerization, the polymer was collected by filtration and dried at 80 ° C. under reduced pressure for 10 hours to obtain 63.0 g of an ethylene / 1-hexene copolymer. The polymerization activity is 31.5 kg / mmol-Zr, and the obtained copolymer has a density of 0.943 g / cm ³ , 190 ° C., MFR measured under a load of 2.16 kg, 5.1 g / 10 min. The melt tension was 13.7 g.

[Comparative Example 1]
Preparation of solid catalyst component (X-3) 34.8 mL of toluene was placed in a 200 mL glass flask purged with nitrogen,
Under stirring, the toluene slurry (3.0 g in terms of solid part) of the solid component (S1) prepared above was charged and heated to 80 ° C. Next, 48.9 mL of a toluene solution of ethylenebis (indenyl) zirconium dichloride (0.0015 mmol / mL in terms of Zr atom) was added dropwise over 20 minutes and reacted at 80 ° C. for 2 hours. Then, after cooling to room temperature, the supernatant was removed by decantation, washed with hexane three times, and 150 mL of decane was added to prepare a decane slurry of the solid catalyst component (X-3). When a part of the resulting decane slurry of the solid catalyst component (X-3) was collected to examine the concentration, the Zr concentration was 0.027 mg / mL, and the Al concentration was 1.91 mg / mL.

In Polymerization <br/> Example 1, in place of the solid catalyst component (X-1), except for using 0.00025mmol solid catalyst component prepared above and (X-3) in terms of zirconium atom is Example 1 In the same manner, copolymerization of ethylene and 1-hexene was carried out.

The obtained polymer was vacuum-dried for 10 hours to obtain 33.4 g of an ethylene / 1-hexene copolymer. The obtained copolymer had a density of 0.933 g / cm ³ , 190 ° C., MFR measured under a load of 2.16 kg, 0.48 g / 10 min, and a melt tension of 7.5 g.

[Comparative Example 2]
In Polymerization <br/> Example 2, in place of the solid catalyst component (X-1), except for using 0.00025mmol solid catalyst component prepared above and (X-3) in terms of zirconium atom Example 2 In the same manner, copolymerization of ethylene and 1-hexene was carried out.

The obtained polymer was vacuum-dried for 10 hours to obtain 31.7 g of an ethylene / 1-hexene copolymer. The obtained copolymer had a density of 0.934 g / cm ³ , 190 ° C., MFR measured under a load of 2.16 kg of 0.97 g / 10 min, and a melt tension of 4.6 g.

[Comparative Example 3]
In Polymerization <br/> Example 3, in place of the solid catalyst component (X-1), except for using 0.0005mmol solid catalyst component prepared above and (X-3) in terms of zirconium atom is Example 3 In the same manner, copolymerization of ethylene and 1-hexene was carried out.

The obtained polymer was vacuum-dried for 10 hours to obtain 52.9 g of an ethylene / 1-hexene copolymer. The obtained copolymer had a density of 0.944 g / cm ³ , 190 ° C., MFR measured under a load of 2.16 kg, 16.6 g / 10 min, and a melt tension of 1.0 g.

[Comparative Example 4]
In Polymerization <br/> Example 5, in place of the solid catalyst component (X-2), except for using 0.000975mmol solid catalyst component prepared above and (X-3) in terms of zirconium atom is Example 5 In the same manner, copolymerization of ethylene and 1-hexene was carried out.

As a result, 70.2 g of an ethylene / 1-hexene copolymer was obtained. The polymerization activity is 72.0 kg / mmol-Zr, and the obtained copolymer has a density of 0.942 g / cm ³ , 190 ° C., MFR measured under a load of 2.16 kg, 7.3 g / 10 min. The melt tension was 3.3 g.

  From the comparison of Example 1-5 and Comparative Example 1-4, when the solid catalyst for olefin polymerization of the present invention is used, the effect of improving the melt tension is easily understood.

1 that is plotted with respect to MFR / MT in the examples and comparative examples of the present invention, it can be easily understood that there is an effect of improving the melt tension when the solid catalyst for olefin polymerization of the present invention is used.

It is drawing which plotted about MFR * MT in the Example and comparative example in this invention.

Claims (5)

A solid carrier;
(A) (a) Compound represented by the following formula (II), (III) or (IV)

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 group. Two substituents on the same carbon, silicon, germanium, and tin atoms may be bonded to each other to form a ring. t ¹ and t ² are each independently a hydrogen atom, a halogen atom, a C ₁ -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 formula (IV), R ⁷ , t ¹ , t ² , M are the same as defined in formula (II), and R ^{8 to} R ¹⁹ are independently a hydrogen atom, a halogen atom, C _{1 to} C ₂₀ alkyl groups, C ₃ -C ₂₀ cycloalkyl groups, C ₂ -C ₂₀ alkenyl groups, C ₆ -C ₂₀ aryl groups, or C ₇ -C ₂₀ arylalkyl groups, silicon, halogen or germanium Atoms may be included, and adjacent substituents from R ^{8 to} R ¹⁹ may be bonded to each other to form a ring. ],
(B) an organoaluminum oxy compound, and (c) a polyfunctional organic halide represented by the general formula (I),

[In the formula (I), R is a divalent radical containing one or more halogen atoms, o, p are each 1
In it, Q ¹ and Q ^2, shows the -OH together. And a solid transition metal catalyst component obtained by contacting, if necessary,
(B) An olefin polymerization catalyst comprising an organoaluminum compound. A solid carrier;
(A) (a) a compound represented by the following formula (II), (III) or (IV),

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 group. Two substituents on the same carbon, silicon, germanium, and tin atoms may be bonded to each other to form a ring. t ¹ and t ² are each independently a hydrogen atom, a halogen atom, a C ₁ -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 formula (IV), R ⁷ , t ¹ , t ² , M are the same as defined in formula (II), and R ^{8 to} R ¹⁹ are independently a hydrogen atom, a halogen atom, C _{1 to} C ₂₀ alkyl group, C ₃ cycloalkyl group ~ C _20, C ₂ -C ₂₀ alkenyl group, aryl group C ₆ ~ C ₂₀ or C ₇ arylalkyl group -C ₂₀ silicon, halogen or germanium Can contain atoms, R ⁸ ~
Adjacent substituents up to R ¹⁹ may combine with each other to form a ring. ],
(B) an organoaluminum oxy compound, and (c) a polyfunctional organic halide represented by the general formula (I)

[In the formula (I), R is a divalent radical containing one or more halogen atoms, o, p are each 1
In it, Q ¹ and Q ^2, shows the -OH together. And (d) a solid transition metal catalyst component obtained by contacting an organoaluminum compound, and if necessary,
(B) An olefin polymerization catalyst comprising an organoaluminum compound. The olefin polymerization catalyst according to claim 1 or 2, wherein the polyfunctional organic halide (c) represented by the general formula (I) is tetrafluorohydroquinone. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 3. The method for producing an olefin polymer according to claim 4, wherein the olefin polymer is a copolymer of ethylene and α-olefin.

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