WO2012118233A1 - Addition polymerization method, prepolymerized catalytic component for addition polymerization, and method for producing addition polymer - Google Patents

Addition polymerization method, prepolymerized catalytic component for addition polymerization, and method for producing addition polymer Download PDF

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WO2012118233A1
WO2012118233A1 PCT/JP2012/056042 JP2012056042W WO2012118233A1 WO 2012118233 A1 WO2012118233 A1 WO 2012118233A1 JP 2012056042 W JP2012056042 W JP 2012056042W WO 2012118233 A1 WO2012118233 A1 WO 2012118233A1
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group
atom
methyl
polymerization
tert
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PCT/JP2012/056042
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French (fr)
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Naoko Ochi
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Sumitomo Chemical Company, Limited
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the present invention relates to an addition polymerization method, a prepolymerized catalyst component for addition polymerization, and a method for producing an addition polymer.
  • Patent Document 1 describes modified particles obtained by using silica gel, an organozinc compound,
  • an olefin is polymerized using a catalyst comprising the particles, a transition metal compound and an or anoaluminum.
  • Patent Document 2 describes a method in which an olefin is prepolymerized by a catalyst obtained by using specific particles as one of catalyst components to obtain a prepolymerized catalyst component for olefin polymerization, and then main polymerization is performed using the prepolymerized catalyst component.
  • Patent Document l JP-A-2003- 171413
  • Patent Document 2 JP-A-2002-293817 Summary of the Invention
  • An object of the present invention is to provide a polymerization method which gives an addition polymer and a prepolymerized catalyst component for addition polymerization that contain less fine powders,
  • the present invention is directed to a method for addition polymerizing monomers capable of addition polymerization, the method comprises the following steps:
  • M 1 is a transition metal atom of Group 4;
  • L 1 is a group having a cyclop entadiene type anionic frame or a group containing a hetero atom!
  • X 1 is a halogen atom, a hydrocarbyloxy group, or a hydrocarbyl group other than groups having a cyclopentadiene type anionic frame;
  • a is a number satisfying 0 ⁇ a ⁇ 3!
  • b is a number satisfying 0 ⁇ b ⁇ 3; when a is more than 1, one L 1 may be linked to another L 1 either directly or by a group
  • R 1 is a hydrocarbyl group having 1 to 30 carbon atoms which may have a substituent
  • R 2 is an alkylene group having 1 to 20 carbon atoms which may have a substituent
  • M 2 is a hydrogen atom or an alkali metal atom
  • R 3 is an alkylene group having 1 to 20 carbon atoms which may have a substituent
  • R 4 is a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent
  • n is a number of 1 to 100; when n is more than 1, R 2
  • the present invention is directed to a prepolymerized catalyst component for addition polymerization obtained by the above method when the above method is a prepolymerization method.
  • the present invention is directed to a method for producing an addition polymer, using the prepolymerized catalyst component for addition polymerization and if necessary, an organoaluminum compound (C).
  • the present invention is directed to a prepolymerized catalyst component for addition polymerization, wherein the cumulative weight fraction of a prepolymerized catalyst component for addition polymerization having a particle diameter of 60 pm or less is 7% or less.
  • the compound (A) to be used in the present invention is selected from among transition metal compounds and their ⁇ - ⁇ type transition metal compound dimers.
  • Examples of the transition metal compound or ⁇ - oxo type transition metal compound dimer thereof include a transition metal compound represented by Formula [l] described below or a ⁇ - ⁇ type transition metal compound dimer thereof
  • M 1 is a transition metal atom of Group 4;
  • L 1 is a group having a cyclopentadiene type anionic frame or a group containing a hetero atom;
  • X 1 is a halogen atom, a hydrocarbyloxy group, or a hydrocarbyl group other than groups having a cyclopentadiene type anionic frame;
  • a is a number satisfying 0 ⁇ a ⁇ 3!
  • b is a number satisfying 0 ⁇ b ⁇ 3! when a is more than 1, one L 1 may be linked to another L 1 either directly or by a group
  • M 1 in Formula [l] is a titanium atom, a zirconium atom or a hafnium atom, and more preferably a zirconium atom.
  • Examples of the group having a cyclopentadiene type anionic frame of L 1 in Formula [l] include an optionally substituted cyclopentadienyl group, an optionally substituted indenyl group and an optionally substituted fluorenyl group.
  • L 1 examples include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a n- butylcyclopentadienyl group, a tert-butylcyclopentadienyl group, a 1,2- dimethylcyclopentadienyl group, a 1,3-dimethylcyclopentadienyl group, a 1- methyl-2-ethylcyclopentadienyl group, a l-methyl-3-ethylcyclopentadienyl group, a l-tert-butyl-2-methylcyclopentadienyl group, a l-tert-butyl-3- methylcyclopentadienyl group, a l-methyl-2-isopropylcyclopentadienyl group, a l-methyl-3-isopropylcyclopentadienyl
  • hapticity ⁇ of the ligand contained in the group having a cyclopentadiene type anionic frame used in L 1 in Formula [l] there is no particular limitation on hapticity ⁇ of the ligand contained in the group having a cyclopentadiene type anionic frame used in L 1 in Formula [l], and the hapticity ⁇ of the ligand may be any value which is available in the group having a cyclopentadiene type anionic frame.
  • Examples of the hapticity of the ligand include five, four, three, two and one.
  • the hapticity of the ligand is preferably five, three or one, and more preferably five or three.
  • Examples of the hetero atom in the group containing a hetero atom of L 1 in Formula [l] include an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom, and the group is preferably an alkoxy group, an aryloxy group, a thioalkoxy group, a thioaryloxy group, an alkylamino group, an arylamino group, an alkylphosphino group, an arylphosphino group, an chelating ligand, or an aromatic heterocyclic group or aliphatic heterocyclic group containing an oxygen atom, a sulfur atom, an nitrogen atom and/or a phosphorus atom in its ring.
  • Examples of the group containing a hetero atom of L 1 in Formula [l] include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group, a 2-methylphenoxy group, 2,6-dimethylphe oxy group, a 2,4,6-trimethylphenoxy group, a 2-ethylphenoxy group, a 4-n-propylphenoxy group, a 2-isopropylphenoxy group, a 2,6-diisopropylphenoxy group, a 4-sec- butylphenoxy group, a 4-tert-butylphenoxy group, a 2,6-di-sec-butylphenoxy group, a 2-tert"butyl-4-methylphenoxy group, a 2,6-di-tert-butylphenoxy group, a 4-methoxyphenoxy group, a 2,6-dimethoxyphenoxy group, a 3,5- dimethoxyphenoxy group, a 2-chlorophen
  • dimethylphosphino group a 2-(2-oxy- l-propyl)phenoxy group, catechol, resorcinol, 4-isopropylcatechol, 3-methoxycatechol, a 1,8-dihydroxynaphthyl group, a 1,2-dihydroxynaphthyl group, a 2,2'-biphenyldiol group, a l, l'-bi-2- naphthol group, a 2,2'-dihydroxy6,6'-dimethylbiphenyl group, a 4,4',6,6'- tetra-tert-butyl-2,2'-methylenediphenoxy group and a 4,4',6,6'-tetramethyl- 2,2'-isobutylidenediphenoxy group.
  • Examples of the group containing a hetero atom also include a group represented by Formula [6]:
  • R 7 each independently represents a hydrogen atom, a halogen atom or a hydrocarbyl group, or any two of R 7 groups are linked to one another to form a hydrocarbylene group.
  • R 7 in Formula [6] examples include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert- butyl group, a cyclopropyl group, a cyclobutyl group, a cycloheptyl group, a cyclohexyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group and a benzyl group.
  • Examples of the group containing a hetero atom also include a group represented by Formula [7]:
  • R 8 group each independently represents a hydrogen, atom, a halogen atom, a hydrocarbyl group, a halogenated hydrocarbyl group, a hydrocarbyloxy group, a silyl group or an amino group, or any two or more of R 8 groups are linked to one another to form a ring structure.
  • R 8 in Formula [7] examples include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a 1- naphthyl group, a 2-naphthyl group, a tert-butyl group, a 2,6- dimethylphenyl group, a 2-fluorenyl group, a 2-methylphenyl group, a 4- trifluoromethylphenyl group, a 4-methoxyphenyl group, a 4-pyridyl group, a cyclohexyl group, a 2-isopropylphenyl group, a benzyl group, a methyl group, a triethylsilyl group, a diphenylmethylsilyl group, a 1 -methyl- 1-phenylethyl group, a 1, 1-dimethylpropyl group, a 2-chloro henyl group and
  • the chelating ligand of L 1 in Formula [l] means a ligand having a plurality of coordination sites, and examples of the ligand include
  • acetylacetonate diimine, oxazoline, bisoxazoline, terpyridine, acylhydrazone, diethylenetriamine, triethylenetetramine, porphyrin, crown ether and cryptate.
  • heterocyclic group of L 1 in Formula [l] examples include a pyridyl group, an N-substituted imidazolyl group and an N-substituted indazolyl group. Among them, a pyridyl group is preferred.
  • L 1 groups in Formula [l] are linked to each other by a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom (that is, when groups having a cyclopentadiene type anionic frame are linked to each other by its residue, when groups containing a hetero atom are linked to each other by its residue, or when a group having a cyclopentadiene type anionic frame and a group containing a hetero atom are linked to each other by its residue), its residue is preferably a divalent residue in which the atom linked to L 1 is a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, and the number of atoms linking two L 1 groups is 3 or less.
  • alkylene groups such as a methylene group, an ethylene group and a propylene group
  • substituted alkylene groups such as a dimethylmethylene group (an isopropylidene group) and a diphenylmethylene group
  • ' substituted silylene groups such as a silylene group, a dimethylsilylene group, a diethylsilylene group, a diphenylsilylene group, a tetramethyldisilylene group and a
  • dimethoxysilylene group dimethoxysilylene group
  • hetero atoms such as a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom.
  • a methylene group an ethylene group, a dimethylmethylene group
  • dimethoxysilylene group is particularly preferred.
  • Examples of the halogen atom of X 1 in Formula [l] include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • Examples of the hydrocarbyl group of X 1 include an alkyl group, an ar alkyl group, an aryl group, and an alkenyl group, and among them, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkenyl group having 3 to 20 carbon atoms is preferable.
  • alkyl group having 1 to 20 carbon atoms examples include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n- butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a n- pentyl group, a neopentyl group, an amyl group, a n-hexyl group, a n-octyl group, a n-decyl group, a n-dodecyl group, a n-pentadecyl group, and a n- eicosyl group, and among them, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an isobutyl group or an amyl group is more preferable.
  • any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
  • a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
  • the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, and a perbromopropyl group.
  • alkyl groups may have alkoxy groups such as a methoxy group and an ethoxy group! aryloxy groups such as a phenoxy group; or aralkyloxy groups such as a benzyloxy group as a substituent.
  • Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group, a (2-methylphenyl)methyl group, a (3-methylphenyl)methyl group, a (4-methylphenyl)methyl group, a (2,3-dimethylphenyl)methyl group, a (2,4-dimethylphenyl)methyl group, a (2,5-dimethylphenyl)methyl group, a (2,6-dimethylphenyl)methyl group, a (3,4-dimethylphenyl)methyl group, a (3,5-dimethylphenyl)methyl group, a (2,3,4-trimethylphenyl)methyl group, a (2,3,5-trimethylphenyDmethyl group, a (2,3,6-trimethylphenyl)methyl group, a (3,4,5-trimethylphenyl)methyl group, a (2,4,6-trimethylphenyDmethyl group, a (2,3,4,5-trimethylphenyDmethyl group, a (2,
  • anthracenylmethyl group and a benzyl group is more preferabe.
  • These aralkyl groups may have halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group and an ethoxy group; aryloxy groups such as a phenoxy group; or aralkyloxy groups such as a benzyloxy group as a substituent.
  • Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, a 2,6-xylyl group, a 3,4-xylyl group, a 3,5-xylyl group, a 2,3,4-trimethylphenyl group, a 2,3,5- trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 2,4,6- trimethylphenyl group, a 3,4,5-trimethylphenyl group, a 2,3,4,5- tetramethylphenyl group, a 2,3,4,6-tetramethylphenyl group, a 2,3,5,6- tetramethylphenyl group, a pentamethylphenyl group, an ethylphenyl group, a n-prop
  • aryl groups may have halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group and an ethoxy group; aryloxy groups such as a phenoxy group; or aralkyloxy groups such as a benzyloxy group as a substituent.
  • halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom
  • alkoxy groups such as a methoxy group and an ethoxy group
  • aryloxy groups such as a phenoxy group
  • aralkyloxy groups such as a benzyloxy group as a substituent.
  • alkenyl group having 3 to 20 carbon atoms examples include an allyl group, a metallyl group, a crotyl group and a l,3-diphenyl-2- propenyl group, and among them, an allyl group or a metallyl group is more preferable.
  • Examples of the hydrocarbyloxy group of X 1 in Formula [l] include an alkoxy group, an aralkyloxy group and an aryloxy group, and among them, an alkoxy group having 1 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms is more preferabe.
  • Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentoxy group, a neopentoxy group, a n-hexoxy group, a n-octoxy group, a n-dodesoxy group, a n-pentadesoxy group, and a n-icosoxy group, and among them, a methoxy group, an ethoxy group, an isopropoxy group or a tert-butoxy group is preferabe.
  • alkoxy groups may have halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group and an ethoxy group; aryloxy groups such as a phenoxy group; or aralkyloxy groups such as a benzyloxy group as a substituent.
  • halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom
  • alkoxy groups such as a methoxy group and an ethoxy group
  • aryloxy groups such as a phenoxy group
  • aralkyloxy groups such as a benzyloxy group as a substituent.
  • Examples of the aralkyloxy group having 7 to 20 carbon atoms include a benzyloxy group, a (2-methylphenyl)methoxy group, a (3- methylphenyDmethoxy group, a (4-methylphenyl)methoxy group, a (2,3- dimethylphenyDmethoxy group, a (2,4-dimethylphenyl)methoxy group, a (2,5-dimethylphenyl)methoxy group, a (2,6-dimethylphenyl)methoxy group, a (3,4-dimethylphenyl)methoxy group, a (3,5-dimethylphenyl)methoxy group, a (2,3,4-trimethylphenyl)methoxy group, a (2,3,5-trimethylphenyl)methoxy group, a (2,3,6-trimethylphenyDmethoxy group, a (2,4,5- trimethylpheny methoxy group, a (2,4,6-trimethylphen
  • aralkyloxy groups may have halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group and an ethoxy group; aryloxy groups such as a phenoxy group; or aralkyloxy groups such as a benzyloxy group as a substituent.
  • Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a 2 -methylphenoxy group, a 3-methylphenoxy group, a 4- methylphenoxy group, a 2,3-dimethylphenoxy group, a 2,4-dimethylphenoxy group, a 2,5-dimethylphenoxy group, a 2,6-dimethylphenoxy group, a 3,4- dimethylphenoxy group, a 3,5-dimethylphenoxy group, a 2-tert-butyl-3- methylphenoxy group, a 2-tert-butyl"4-methylphenoxy group, a 2-tert-butyl- 5-methylphenoxy group, a 2-tert-butyl-6-methylphenoxy group, a 2,3,4- trimethylphenoxy group, a 2,3,5-trimethylphenoxy group, a 2,3,6- trimethylphenoxy group, a 2,4,5-trimethylphenoxy group, a 2,4,6- trimethylphenoxy group, a 2-tert"buty
  • aryloxy groups may have halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group and an ethoxy group; aryloxy groups such as a phenoxy group; or aralkyloxy groups such as a benzyloxy group as a substituent.
  • halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom
  • alkoxy groups such as a methoxy group and an ethoxy group
  • aryloxy groups such as a phenoxy group
  • aralkyloxy groups such as a benzyloxy group as a substituent.
  • X 1 in Formula [l] is more preferably a chlorine atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a trifluoromethoxy group, a phenyl group, a phenoxy group, a 2,6-di-tert-butylphenoxy group, a 3,4,5-trifluorophenoxy group, a
  • pentafluorophenoxy group a 2,3,5,6-tetrafluoro-4- pentafluorophenylphenoxy group or a benzyl group.
  • a in Formula [l] is a number satisfying 0 ⁇ a ⁇ 3, and b is a number satisfying 0 ⁇ b ⁇ 3.
  • a and b are appropriately selected according to the valance of M 1 .
  • M 1 is a titanium atom, a zirconium atom, or a hafnium atom, a is preferably 2 and also b is preferably 2.
  • Examples of the compound represented by Formula [l] in which a transition metal atom is a titanium atom include
  • cyclopentadienyl(fluorenyl)titanium dichloride indenyl(fluorenyl)titanium dichloride, pentamethylcyclopentadienyl(indenyl)titanium dichloride, pentamethylcyclopentadienyl(fluorenyl)titanium dichloride,
  • dimethylsilylenebis(indenyl)titanium dichloride dimethylsilylenebis(2- methylindenyDtitanium dichloride, dimethylsilylenebis(2-tert- butylindenyDtitanium dichloride, dimethylsilylenebis(2,3- dimethylindenyDtitanium dichloride, dimethylsilylenebis(2,4,7- trimethylindeny titanium dichloride, dimethylsilylenebis(2-methyl-4- isopropylindenyDtitanium dichloride, dimethylsilylenebis(4,5- benzindenyDtitanium dichloride, dimethylsilylenebis(2-methyl-4,5- benzindenyl)titanium dichloride, dimethylsilylenebis(2- phenylindenyl)titanium dichloride, dimethylsilylenebis(4- phenylindeny titanium dichloride, dimethylsilylenebis(2-methyl-4- phenylindenyl)titan
  • dimethy lsily le ne (methy Icy clop e ntadieny 1) (inde nyl) titanium dichloride , dimethylsilylene(n-butylcyclopentadienyl) (indenyl)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl) (indenyl)titanium dichloride, dimethylsilylene(cyclopentadienyl) (fluorenyl)titanium dichloride,
  • cyclopentadienyltitanium trichloride pentamethylcyclopentadienyltitanium trichloride, cyclopentadienyl(dimethylamide)titanium dichloride,
  • cyclopentadienyl(phenoxy)titanium dichloride cyclopentadienyl(2,6- dimethylphenyDtitanium dichloride, cyclopentadienyl(2,6- diisop ropy lp he nyl) titanium dichloride , cyclop e ntadieny 1(2 , 6 - di - tert - butylpheny titanium dichloride, pentamethylcyclopentadienyl(2,6- dimethylphenyDtitanium dichloride, pentamethylcyclopentadienyl(2,6- diisopropylphenyOtitanium dichloride, pentamethylcyclopentadienyl(2,6- tert-butylphenyl)titanium dichloride, indenyl(2,6- diisopropylpheny titanium dichloride, fluore nyl (2, 6- diisopropy
  • dimethylsilylene(cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy)titanium dichloride
  • dimethylsilylene(cyclopentadienyl) (5-methyl-3-phenyl-2- phenoxy)titanium dichloride
  • dimethylsilylene(cyclopentadienyl) (3-tert- butyldimethylsilyl- 5 - methyl- 2 -phenoxy)titanium dichloride
  • dimethylsilylene(cyclopentadienyl) (5-methyl-3-trimethylsilyl-2- phenoxy)titanium dichloride
  • dimethylsilylene(cyclopentadienyl) (3-tert- butyl- 5 -methoxy- 2 -phenoxy)titanium dichloride
  • dimethylsilylene(cyclopentadienyl) (3-tert-butyl-5-chloro-2- phenoxy)titanium dichloride
  • dimethylsilylene(cyclopentadienyl) (3,5- diamyl-2-phenoxy)titanium dichloride
  • dimethylsilylene(cyclopentadienyl) (3-phenyl-2-phenoxy)titanium dichloride
  • dimethylsilylene(cyclopentadienyl) ( 1 - naphthoxy - 2 -yDtitanium dichloride
  • dimethylsilylene(methylcyclopentadienyl) (5-methyl-3-phenyl-2- phenoxy)titanium dichloride
  • dimethylsilylene(methylcyclopentadienyl) (3- tert-butyldimethylsilyl-5"methyl-2-phenoxy)titanium dichloride
  • dimethylsilylene(methylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2- phenoxy)titanium dichloride
  • dimethylsilylene(methylcyclopentadienyl) (3- tert-butyl-5-methoxy-2-phenoxy)titanium dichloride
  • dime thy lsilyle ne (n -b uty Icy clop e ntadie ny 1) (2 -p he noxy) titanium dichloride , dimethylsilylene(n-butylcyclopentadienyl) (3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl) (3,5-dimethyl-2- phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl) (3- tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(n- butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl) (3,5-di-tert-butyl"2-
  • dichloride dimethylsilylene(n-butylcyclopentadienyl) (3-tert-butyl-5-chloro- 2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl) (3,5-diamyl-2-phenoxy)titanium dichloride, dimethylsilylene(n- butylcyclopentadienyl) (3-phenyl-2-phenoxy)titanium dichloride,
  • dimethy lsily le ne (n- buty Icy elope ntadie ny 1) ( 1 - nap hthoxy - 2 - y titanium dichloride,
  • dimethylsilylene(tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2- phenoxy)titanium dichloride
  • dimethylsilylene(tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride
  • dimethylsilylene(tert- butylcyclopentadienyl) (3,5-diamyl-2-phenoxy)titanium dichloride
  • dimethylsilylene(tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy)titanium dichloride
  • dimethylsilylene(tert-butylcyclopentadienyl) (l-naphthoxy-2- yl)titanium dichloride
  • dimethylsilylene(tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2- phenoxy)titanium dichloride
  • dimethylsilylene(tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride
  • dimethylsilylene(trimethylsilylcyclopentadienyl) (2-phenoxy)titanium dichloride dimethylsilylene (trimethylsilylcy clopentadieny 1) (3 ⁇ methyl- 2 - phenoxy)titanium dichloride,
  • dimethylsilylene(indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl) (3-tert-butyl-5-methoxy-2- phenoxy)titanium dichloride, dimethylsilylene(indenyl) (3-tert-butyl-5- chloro-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl) (3,5-diamyl- 2-phenoxy)titanium dichloride, dimethylsilylene(indenyl) (3-phenyl-2- phenoxy)titanium dichloride, dimethylsilylene(indenyl) (l-naphthoxy-2- yl)titanium dichloride,
  • dimethylsilylene(fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl) (3-tert-butyl-5-methoxy-2- phenoxy)titanium dichloride, dimethylsilylene(fluorenyl) (3-tert-butyl _ 5- chloro-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl) (3,5- diamyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl) (3- phenyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl) (l- naphthoxy-2-yl)titanium dichloride,
  • diethylsilylene diphenylsilylene
  • diphenylsilylene diphenylsilylene
  • methoxysilylene diphenylsilylene
  • Examples of the compound represented by Formula [l] in which a transition metal atom is a zirconium atom or a hafnium atom include compounds in which
  • titanium in the above-mentioned compound is replaced by “zirconium” or “hafnium”, respectively.
  • Examples of the transition metal compound represented by Formula [l] also include the following compounds.
  • transition metal compound further include, in addition to these compounds, compounds in which the titanium atom of the above-mentioned compounds is replaced by a zirconium atom or a hafnium atom.
  • transition metal compound further include compounds in which "dichloride" in the above-mentioned compounds is replaced by "difluoride", “dibromide", “diiodide", “dimethyl, "diethyl", “diisopropyl", “diphenyl", “dibenzyl", “dimethoxide", “diethoxide”, “di(n- propoxide)", “di(isopropoxide)", “diphenoxide”, or “di(pentafluorophenoxide)", and compounds in which "trichloride" in the above-mentioned compounds is replaced by "trifluoride", “tribromide", “triiodide", “trimethyl", “triethyl", “triisopropyl", "triphenyl", “tribenzyl", “trimethoxide", “triethoxide”, “tri(n- propoxide)", "tri(isopropoxide)", "triphenoxide", or
  • transition metal compounds may be used alone, or two or more kinds of them may be used in combination.
  • the compounds (A) to be used in the present invention are preferably compounds in which M 1 is zirconium, and transition metal compounds which have at least one group having a cyclopentadiene type anionic frame as L 1 in
  • zirconium compounds which have two groups having a cyclopentadiene type anionic frame as L 1 in Formula [l], L 1 groups being linked to each other by a group containing a carbon atom, a silicon atom, an oxygen atom, a sulfur atom or a phosphorus atom, are particularly preferable.
  • the transition metal compound represented by Formula [l] can be produced by the production methods described in JP-A-6-340684, JP-A-7- 258321, and International Publication No. WO 95/00562 and the like.
  • the organic compound (D) to be used in the present invention is specifically an organic compound represented by Formula [2] :
  • R 1 is a hydrocarbyl group having 1 to 30 carbon atoms which may have a substituent
  • R 2 is an alkylene group having 1 to 20 carbon atoms which may have a substituent
  • M is a hydrogen atom or an alkali metal atom
  • R 3 is an alkylene group having 1 to 20 carbon atoms which may have a substituent
  • R 4 is a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent
  • n is a number of 1 to 100; when n is more than 1, R 2 groups may be the same or different.
  • Examples of the hydrocarbyl group having 1 to 30 carbon atoms which may have a substituent of R 1 include an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aralkyl group having 7 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent and the like.
  • Examples of the alkyl group having 1 to 30 carbon atoms which may have a substituent of R 1 include an alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms which has a halogen atom as a substituent, an alkyl group having 1 to 30 carbon atoms which has a substituted silyl group as a substituent, an alkyl group having 1 to 30 carbon atoms which has a substituted amino group as a substituent, an alkyl group having 1 to 30 carbon atoms which has a hydrocarbyloxy group as a substituent and the like.
  • alkyl group having 1 to 30 carbon atoms of R 1 examples include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a neopentyl group, an isopentyl group, a n-hexyl group, a n-heptyl group, a n- octyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group, a n-tridecyl group, a n-tetradecyl group, a n-pentadecyl group, a n- hexadecyl group, a n-hepta
  • Examples of the alkyl group having 1 to 30 carbon atoms which has a halogen atom as a substituent of R 1 include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, an iodomethyl group, a diiodomethyl group, a triiodomethyl group, a fluoroethyl group, a
  • difluoroethyl group a trifluoroethyl group, a tetrafluoroethyl group, a pentafluoroethyl group, a chloroethyl group, a dichloroethyl group, a trichloroethyl group, a tetrachloroethyl group, a pentachloroethyl group, a bromoethyl group, a dibromoethyl group, a tribromoethyl group, a
  • tetrabromoethyl group a pentabromoethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorododecyl group, a perfluoropentadecyl group, a perfluoroeicosyl group, a perfluorotriacontyl group, a perchloropropyl group, a perchlorobutyl group, a perchloropentyl group, a perchlorohexyl group, a perchlorooctyl group, a perchlorododecyl group, a
  • perchloropentadecyl group a perchloroeicosyl group, a perchlorotriacontyl group, a perbromopropyl group, a perbromobutyl group, a perbromopentyl group, a perbromohexyl group, a perbromooctyl group, a perbromododecyl group, a perbromopentadecyl group, a perbromoeicosyl group, a
  • alkyl group having 1 to 30 carbon atoms which has a substituted silyl group as a substituent of R 1 include a
  • a b is (trimethylsilyl) ethyl group, a bis(trimethylsilyl)propyl group, a bis(trimethylsilyl)butyl group, a
  • Examples of the alkyl group having 1 to 30 carbon atoms which has a substituted amino group as a substituent of R 1 include a
  • bis(dimethylamino)methyl group bis(dimethylamino)ethyl group, a bis(dimethylamino)propyl group, a bis(dimethylamino)butyl group, a phenylaminomethyl group, a diphenylaminomethyl group and the like.
  • alkyl group having 1 to 30 carbon atoms which has a hydrocarbyloxy group as a substituent of R 1 include a methoxymethyl group, an ethoxymethyl group, a n-propoxymethyl group, an
  • Examples of the aralkyl group having 7 to 30 carbon atoms which may have a substituent of R 1 include an aralkyl group having 7 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms which has a halogen atom as a substituent and the like.
  • Examples of the aralkyl group having 7 to 30 carbon atoms of R 1 include a benzyl group, a (2-methylphenyl)methyl group, a (3- methylphenyDmethyl group, a (4-methylphenyl)methyl group, a (2,3- dimethylphenyDmethyl group, a (2,4-dimethylphenyl)methyl group, a (2,5- dimethylphenyDmethyl group, a (2,6-dimethylphenyl)methyl group, a (3,4- dimethylphenyl)methyl group, a (4,6-dimethylphenyl)methyl group, a (2,3,4- trimethylphenyDmethyl group, a (2,3,5-trimethylphenyDmethyl group, a
  • anthracenylmethyl group a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a diphenylmethyl group, a diphenylethyl group, a diphenylpropyl group, a diphenylbutyl group and the like.
  • Examples of the aralkyl group having 7 to 30 carbon atoms which has a halogen atom as a substituent of R 1 include a 2-fluorobenzyl group, a 3-fluorobenzyl group, a 4-fluorobenzyl group, a 2-chlorobenzyl group, a 3- chlorobenzyl group, a 4-chlorobenzyl group, a 2-bromobenzyl group, a 3- bromobenzyl group, a 4-bromobenzyl group, a 2-iodobenzyl group, a 3- iodobenzyl group, a 4-iodobenzyl group and the like.
  • Examples of the aryl group having 6 to 30 carbon atoms which may have a substituent of R 1 include an aryl group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms which has a halogen atom as a substituent, an aryl group having 6 to 30 carbon atoms which has a substituted silyl group as a substituent, an aryl group having 6 to 30 carbon atoms which has a substituted amino group as a substituent, an aryl group having 6 to 30 carbon atoms which has a hydrocarbyloxy group as a substituent and the like.
  • Examples of the aryl group having 6 to 30 carbon atoms of R 1 include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, a 2,6-xylyl group, a 3,4- xylyl group, a 3,5-xylyl group, a 2,3,4-trimethylphenyl group, a 2,3,5- trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 2,4,6- trimethylphenyl group, a 3,4,5-trimethylphenyl group, a 2,3,4,5- tetramethylphenyl group, a 2,3,4,6-tetramethylphenyl group, a 2,3,5,6- tetramethylphenyl group, a pentamethylphenyl group, an ethylp enyl group,
  • Examples of the aryl group having 6 to 30 carbon atoms which has a halogen atom as a substituent of R 1 include a 2 -fluorophenyl group, a 3- fluorophenyl group, a 4 -fluoro henyl group, a 2-chlorophenyl group, a 3- chlorophenyl group, a 4-chlorophenyl group, a 2-bromophenyl group, a 3- bromophenyl group, a 4-bromophenyl group, a 2-iodophenyl group, a 3- iodophenyl group, a 4-iodophenyl group and the like.
  • Examples of the aryl group having 6 to 30 carbon atoms which has a substituted silyl group as a substituent of R 1 include a trimethylsilylphenyl group, a bis(trimethylsilyl)phenyl group and the like.
  • Examples of the aryl group having 6 to 30 carbon atoms which has a substituted amino group as a substituent of R 1 include a
  • dimethylaminophenyl group a bis(dimethylamino)phenyl group, a
  • Examples of the aryl group having 6 to 30 carbon atoms which has a hydrocarbyloxy group as a substituent of R 1 include a methoxyphenyl group, an ethoxyphenyl group, a n-propoxyphenyl group, an isopropoxyphenyl group, a n-butoxyphenyl group, a sec-butoxyphehyl group, a tert- butqxyphenyl group, a phenoxyphenyl group and the like.
  • R 1 in Formula [2] is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent, and more preferably an alkyl group having 1 to 30 carbon atoms.
  • R 2 represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, and R 2 groups may be the same or different.
  • Examples of the alkylene group having 1 to 20 3 ⁇ 4arbon atoms which may have a substituent of R 2 include an alkylene group having 1 to 20 carbon atoms ,an alkylene group having 1 to 20 carbon atoms which has a halogen atom as a substituent, an alkylene group having 1 to 20 carbon atoms which has a substituted silyl group as a substituent, an alkylene group having 1 to 20 carbon atoms which has a substituted amino group as a substituent, an alkylene group having 1 to 20 carbon atoms which has a hydrocarbyloxy group as a substituent and the like.
  • alkylene group having 1 to 20 carbon atoms of R 2 examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a
  • methylmethylene group a dimethylmethylene group, an ethylmethylene group, an ethylmethylmethylene group, a diethylmethylene group, a propylenemethylene group, a methylethylene group, a dimethylethylene group, a trimethylethylene group, a tetramethylethylene group and the like.
  • lilxamples of the alkylene group having 1 to 20 carbon atoms which has a halogen atom as a substituent of R 2 include a fluoromethylene group, a difluoromethylene group, a chloromethylene group, a dichloromethylene group, a bromomethylene group, a dibromomethylene group, a
  • iodomethylene group a diiodomethylene group, a fluoroethylene group, a difluoroethylene group, a trifluoroethylene group, a tetrafluoroethylene group, a chloroethylene group, a dichloroethylene group, a trichloroethylene group, a tetrachloroethylene group, a bromoethylene group, a
  • dibromoethylene group a tribromoethylene group, a tetrabromoethylene group, a perfluoropropylene group, a perfluorobutylene group, a
  • perfluoropentylene group a perfluorohexylene group, a perfluorooctylene group, a perfluorododecylene group, a perfluoropentadecylene group, a perfluoroeicosylene group, a perchloropropylene group, a perchlorobutylene group, a perchloropentylene group, a perchlorohexylene group, a
  • perchlorooctylene group a perchlorododecylene group, a
  • perchloropentadecylene group a perchloroeicosylene group, a perbromopropylene group, a perbromobutylene group, a perbromopentylene group, a perbromohexylene group, a perbromooctylene group, a
  • perbromododecylene group a perbromopentadecylene group, a
  • Examples of the alkylene group having 1 to 30 carbon atoms which has a substituted silyl group as a substituent of R 2 include a
  • bis(trimethylsilyl)methylene group a bis(trimethylsilyl)ethylene group, a bis(trimethylsilyl)propylene group, a bis(trimethylsilyl)butylene group, a triphenylsilylmethyl group and the like.
  • Examples of the alkylene group having 1 to 30 carbon atoms which has a substituted amino group as a substituent of R 2 include a
  • dimethylaminomethylene group a dimethylaminoethylene group, a dimethylaminopropylene group, a dimethylaminobutylene group, a bis(dimethylamino)methylene group, a bis(dimethylamino)ethylene group, a bis(dimethylamino)propylene group, a bis(dimethylamino)butylene group, a phenylaminomethylene group, a diphenylaminomethylene group and the like.
  • alkylene group having 1 to 20 carbon atoms which has a hydrocarbyloxy group as a substituent of R 2 include a
  • methoxymethylene group an ethoxy methylene group, a n- propoxymethylene group, an isopropoxy methylene group, a n- butoxymethylene group, a sec-butoxymethylene group, a tert- butoxy methylene group, a phenoxymethylene group, a methoxyethylene group, an ethoxy ethylene group, a n-propoxyethylene group, an
  • R 2 in Formula [2] is preferably an alkylene group having 1 to 20 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, or a hexylene group, and still more preferably an ethylene group.
  • M 2 represents an alkali metal atom.
  • M 2 is preferably a sodium atom or a potassium atom, and more preferably a sodium atom.
  • R 3 represents an alkylene group having 1 to 20 carbon atoms which may have a substituent.
  • Examples of the alkylene group having 1 to 20 carbon atoms which may have a substituent of R 3 include the same alkylene groups as those exemplified in R 2 .
  • R 3 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, or a hexylene group, and still more preferably a methylene group.
  • R 4 represents a hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent.
  • Examples of the hydrocarbyl group having 1 to 20 carbon atoms which may have a substituent of R 4 include an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent and the like.
  • Examples of the alkyl group having 1 to 20 carbon atoms which may have a substituent of R 4 include an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms which has a halogen atom as a substituent, an alkyl group having 1 to 20 carbon atoms which has a substituted silyl group as a substituent, an alkyl group having 1 to 20 carbon atoms which has a substituted amino group as a substituent, an alkyl group having 1 to 20 carbon atoms which has a hydrocarbyloxy group as a substituent and the like.
  • alkyl group having 1 to 20 carbon atoms of R 4 examples include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a neopentyl group, an isopentyl group, a n-hexyl group, a n-heptyl group, a n- octyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group, a n-tridecyl group, a n-tetradecyl group, a n-pentadecyl group, a n- hexadecyl group, a n-hepta
  • Examples of the alkyl group having 1 to 20 carbon atoms which has a halogen atom as a substituent of R 4 include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, an iodomethyl group, a diiodomethyl group, a triiodomethyl group, a fluoroethyl group, a
  • difluoroethyl group a trifluoroethyl group, a tetrafluoroethyl group, a pentafluoroethyl group, a chloroethyl group, a dichloroethyl group, a trichloroethyl group, a tetrachloroethyl group, a pentachloroethyl group, a bromoethyl group, a dibromoethyl group, a tribromoethyl group, a
  • tetrabromoethyl group a pentabromoethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorododecyl group, a perfluoropentadecyl group, a perfluoroeicosyl group, a perchloropropyl group, a perchlorobutyl group, a perchloropentyl group, a perchlorohexyl group, a perchlorooctyl group, a perchlorododecyl group, a perchloropentadecyl group, a perchloroeicosyl group, a perbromopropyl group, a perbromobutyl group, a perbromopentyl group, a
  • alkyl group having 1 to 20 carbon atoms which has a substituted silyl group as a substituent of R 4 include a
  • alkyl group having 1 to 20 carbon atoms which has a substituted amino group of R 4 as a substituent examples include a
  • bis(dimethylamino)methyl group bis(dimethylamino)ethyl group, a bis(dimethylamino)propyl group, a bis(dimethylamino)butyl group, a phenylaminomethyl group, a diphenylaminomethyl group and the like.
  • alkyl group having 1 to 20 carbon atoms which has a hydrocarbyloxy group as a substituent of R 4 include a methoxymethyl group, an ethoxymethyl group, a n-propoxymethyl group, an
  • Examples of the aralkyl group having 7 to 20 carbon atoms which may have a substituent of R 4 include an aralkyl group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms which has a halogen atom as a substituent and the like.
  • Examples of the aralkyl group having 7 to 20 carbon atoms of R 4 include a benzyl group, a (2-methylphenyl)methyl group, a (3- methylpheny methyl group, a (4-methylphenyl)methyl group, a (2,3- dimethylpheny methyl group, a (2,4-dimethylphenyl)methyl group, a (2,5- dimethylpheny methyl group, a (2,6-dimethylphenyl)methyl group, a (3,4- dimethylphenyl)methyl group, a (4,6-dimethylphenyl)methyl group, a (2,3,4- trimethylphenyDmethyl group, a (2,3,5-trimethylphenyl)methyl group, a
  • anthracenylmethyl group a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a diphenylmethyl group, a diphenylethyl group, a diphenylpropyl group, a diphenylbutyl group and the like.
  • Examples of the aralkyl group having 7 to 20 carbon atoms which has a halogen atom as a substituent of R 4 include a 2-fluorobenzyl group, a 3-fluorobenzyl group, a 4-fluorobenzyl group, a 2-chlorobenzyl group, a 3- chlorobenzyl group, a 4-chlorobenzyl group, a 2-bromobenzyl group, a 3- bromobenzyl group, a 4-bromobenzyl group, a 2-iodobenzyl group, a 3- iodobenzyl group, a 4-iodobenzyl group and the like.
  • Examples of the aryl group having 6 to 20 carbon atoms of R 4 include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, a 2,6-xylyl group, a 3,4- xylyl group, a 3,5-xylyl group, a 2,3,4-trimethylphenyl group, a 2,3,5- trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 2,4,6- trimethylphenyl group, a 3,4,5-trimethylphenyl group, a 2,3,4,5- tetramethylphenyl group, a 2,3,4,6-tetramethylphenyl group, a 2,3,5,6- tetramethylphenyl group, a pentamethylphenyl group, an ethylphenyl group, a
  • Examples of the aryl group having 6 to 20 carbon atoms which is substituted with a halogen atom of R 4 include a 2-fluorophenyl group, a 3- fluorophenyl group, a 4-fluorophenyl group, a 2-chlorophenyl group, a 3- chlorophenyl group, a 4-chlorophenyl group, a 2-bromophenyl group, a 3- bromophenyl group, a 4-bromophenyl group, a 2-iodophenyl group, a 3- iodo henyl group, a 4-iodophenyl group and the like.
  • R 4 is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably a methyl group, an ethyl group, a n-propyl group or an isopropyl group.
  • n a number of 1 to 100.
  • n is preferably a number of 1 to 50, more preferably a number of 1 to
  • organic compound (D) examples include polyoxyethylene lauryl ether, polyoxyethylene lauryl ether acetic acid, sodium
  • polyoxyethylene lauryl ether acetate potassium polyoxyethylene lauryl ether acetate, ammonium polyoxyethylene lauryl ether acetate,
  • the organic compound (D) is preferably polyoxyethylene lauryl ether, polyoxyethylene lauryl ether acetic acid, sodium polyoxyethylene lauryl ether acetate, polyoxyethylene lauryl ether sulfuric acid, or sodium
  • polyoxyethylene lauryl ether sulfate and more preferably sodium
  • the activating agent (B) to be used in the present invention may be an agent which can activate the compound (A).
  • a catalyst for addition polymerization is applied to polymerization which forms addition polymer particles (e.g., slurry polymerization, gas phase polymerization, bulk polymerization, etc.)
  • specific particles as one components of a catalyst for addition polymerization because addition polymers having a fixed shape are produced. It is preferable to use, as the specific particles, modified particles of the following (I), (II) or (III):
  • inorganic oxide particles or organic polymer particles wherein M 3 is a Group 12 element; L 2 is a hydrogen atom, a halogen atom or a hydrocarbyl group, and two L 2 groups may be the same or different; R 5 is an electron withdrawing group or a group containing an electron
  • R 5 groups may be the same or different;
  • R 6 is a hydrocarbyl group or a halogenated hydrocarbyl group ;
  • T is a Group 15 element or a Group 16 element;
  • t is a number corresponding to the valence of T;
  • T is a Group 15 element or a Group 16 element;
  • u is a number corresponding to the valence of T'.
  • (III) modified particles produced by bringing inorganic oxide particles or organic polymer particles (d), the aluminoxane (e) and the transition metal compound (A) into contact with one another.
  • M 3 in Formula [3] represents a Group 12 element of the Periodic Table of the elements (the 1989 IUPAC revised edition of inorganic chemical nomenclature).
  • Examples of M 3 include a zinc atom, a cadmium atom and a mercury atom.
  • M 3 is particularly preferably a zinc atom.
  • L 2 is a hydrogen atom, a halogen atom, or a hydrocarbyl group.
  • the halogen atom of L 2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • hydrocarbyl group of L 2 is preferably an alkyl group, an aryl group, or an aralkyl group.
  • the alkyl group of the hydrocarbyl group of L 2 is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a n-pentyl group, a neopentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n- decyl group, a n-dodecyl group, a n-pentadecyl group and a n-eicosyl group, and a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or an isobutyl group is more
  • alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • substituted with a halogen atom can include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorododecyl group, a perfluoropentadecyl group, a perfluoroeicosyl group, a ⁇ , ⁇ -perfluoropropyl group, a ⁇ , ⁇ -perfluorobutyl group, a ⁇ , ⁇ -perfluoropentyl group, a ⁇ , ⁇ -
  • alkyl groups may be substituted with an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group; or an aralkyloxy group such as a benzyloxy group.
  • the aryl group of the hydrocarbyl group of L 2 is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, a 2,6-xylyl group, a 3,4-xylyl group, a 3,5- xylyl group, a 2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 2,4,6-trimethylphenyl group, a 3,4,5- trimethylphenyl group, a 2,3,4,5-tetramethylphenyl group, a 2,3,4,6- tetramethylphenyl group, a 2,3,5,6-tetramethylphenyl group, a 2,3,5,6-t
  • pentamethylphenyl group an ethylphenyl group, a n-propylphenyl group, an isopropylphenyl group, a n-butylphenyl group, a sec-butylphenyl group, a tert-butylphenyl group, an isobutylphenyl group, a n-pentylphenyl group, a neopentylphenyl group, a n-hexylphenyl group, a n-octylphenyl group, a n- decylphenyl group, a n-dodecylphenyl group, a n-tetradecylphenyl group, a naphthyl group and an anthracenyl group, and more preferably a phenyl group.
  • aryl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group; or an aralkyloxy group such as a benzyloxy group.
  • a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom
  • an alkoxy group such as a methoxy group or an ethoxy group
  • an aryloxy group such as a phenoxy group
  • an aralkyloxy group such as a benzyloxy group.
  • the aralkyl group of the hydrocarbyl group of L 2 is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof can include a benzyl group, a (2-methylphenyl)methyl group, a (3- methylpheny methyl group, a (4-methylphenyl)methyl group, a (2,3- dimethylphenyl)methyl group, a (2,4-dimethylphenyl)methyl group, a (2,5- dimethylphenyDmethyl group, a (2,6-dimethylphenyl)methyl group, a (3,4- dimethylpheny methyl group, a (3,5-dimethylphenyl)methyl group, a (2,3,4- trimethylphenyDmethyl group, a (2,3,5-trimethylphenyDmethyl group, a
  • a benzyl group is more preferred. Any of these aralkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group or an ethoxy group! an aryloxy group such as a phenoxy group; or an aralkyloxy group such as a benzyloxy group. [0123]
  • L 2 in Formula [3] is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group.
  • Two L 2 may be the same as or different from each other.
  • T in Formula [4] represents a Group 15 element or a Group 16 element of the Periodic Table of the elements (the 1989 IUPAC revised edition of inorganic chemical nomenclature).
  • Examples of the Group 15 element include a nitrogen atom, a phosphorus atom and the like! and examples of the Group 16 element include an oxygen atom, a sulfur atom and the like.
  • T is preferably a nitrogen atom or an oxygen atom, and particularly preferably an oxygen atom.
  • t in Formula [4] represents the valence of T, and t is 3 when T is the Group 15 element and t is 2 when T is the Group 16 element.
  • T in Formula [5] represents a Group 15 element or a Group 16 element of the Periodic Table of the elements (the 1989 IUPAC revised edition of inorganic chemical nomenclature).
  • Examples of the Group 15 element include a nitrogen atom, a phosphorus atom and the like, ' and examples of the Group 16 element include an oxygen atom, a sulfur atom and the like.
  • T' is preferably a nitrogen atom or an oxygen atom, and particularly preferably an oxygen atom.
  • u in Formula [5] represents the valence of T', and u is 3 when T' is the Group 15 element and u is 2 when T' is the Group 16 element.
  • R 2 in Formula [4] represents an electron withdrawing group or a group containing an electron withdrawing group and, when there are more than one R 2 , they may be the same or different.
  • a substituent constant o of Hammett's rule is known as an indicator of electron withdrawing properties, and examples of the electron withdrawing group include functional groups having a positive substituent constant ⁇ of Hammett's rule.
  • Examples of the electron withdrawing group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfone group, a phenyl group and the like.
  • Examples of the group containing an electron withdrawing group include a halogenated alkyl group, a halogenated aryl group, a (halogenated
  • alkyl)aryl group a cyanated aryl group, a nitrated aryl group, an ester group (an alkoxycarbonyl group, an ar alky loxy carbonyl group, or an aryloxycarbonyl group) and the like.
  • halogenated alkyl group examples include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a difluoromethyl group, a dichloromethyl group, a dibromomethyl group, a diiodomethyl group, a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, a 2,2,2-trifluoroethyl group, a 2,2,2-trichloroethyl group, a 2,2,2-tribromoethyl group, a 2,2,2-triiodoethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3,3-pentachloropropyl group, a 2,2,3,3,3-pentabromopropyl group, a 2,2,3,3,3-pentabromopropyl group, a 2,2,3,3,
  • halogenated aryl group examples include a 2 -fluorophenyl group, a 3 -fluorophenyl group, a 4-fluorophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 3,5- difluorophenyl group, a 2,4,6-trifluorophenyl group, a 3,4,5-trifluorophenyl group, a 2,3,5,6-tetrafluorophenyl group, a pentafluorophenyl group, a 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, a 2,3,5,6-tetrafluoro-4- pentafluorophenylphenyl group, a perfluoro-l-naphthyl group, a perfluoro-2- naphthyl group, a
  • 2- naphthyl group a 2-iodophenyl group, a 3-iodophenyl group, a 4- iodophenyl group, a 2,4-diiodophenyl group, a 2,6-diiodophenyl group, a 3,4- diiodophenyl group, a 3,5-diiodophenyl group, a 2,4,6-triiodophenyl group, a 3,4,5-triiodophenyl group, a 2,3,5, 6-tetraiodophenyl group, a
  • pentaiodophenyl group a 2,3,5,6-tetraiodo-4-triiodomethylphenyl group, a 2,3,5,6"tetraiodo-4-pentaiodophenylphenyl group, a periodo-l-naphthyl group, a periodo-2-naphthyl group and the like.
  • Examples of the (halogenated alkyDaryl group include a 2- (trifluoromethyl)phenyl group, a 3-(trifluoromethyl)phenyl group, a 4- (trifluoromethy phenyl group, a 2,6-bis(trifluoromethyl)phenyl group, a 3,5- bis(trifluoromethyl)phenyl group, a 2,4,6-tris(trifluoromethyl)phenyl group, a 3,4,5-tris(trifluoromethyl)phenyl group and the like.
  • Examples of the cyanated aryl group include a 2-cyanophenyl group, a 3-cyanophenyl group, a 4-cyanophenyl group and the like.
  • nitrated aryl group examples include a 2-nitrophenyl group, a
  • ester group examples include a methoxycarbonyl group, an ethoxycarbonyl group, a normal propoxycarbonyl group, an isopropoxycarbonyl group, a phenoxycarbonyl group, a
  • R 5 is preferably a halogenated hydrocarbyl group, and more preferably a halogenated alkyl group or a halogenated aryl group.
  • R 5 is still more preferably a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3- pentafluoropropyl group, a 2,2,2-trifluoro-l-trifluoromethylethyl group, a l,l-bis(trifluoromethyl)-2,2,2-trifluoroethyl group, a 2-fluorophenyl group, a 3 -fluorophenyl group, a 4-fluorophenyl group, a 2,4-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 3,5-difluorophen
  • trichloromethyl group a 2,2,2-trichloroethyl group, a 2,2,3,3,3- pentachloropropyl group, a 2,2,2-trichloro-l-trichloromethylethyl group, a l,l-bis(trichloromethyl)-2,2,2-trichloroethyl group, a 4-chlorophenyl group, a 2,6-dichlorophenyl group, a 3,5-dichlorophenyl group, a 2,4,6- trichlorophenyl group, a 3,4,5-trichlorophenyl group or a pentachlorophenyl group, particularly preferably a fluoroalkyl group or a fluoroaryl group, and most preferably a trifluoromethyl group, a 2,2,2-trifluoro-l- trifluoromethylethyl group, a l,l-bis(trifluoromethyl)-2,2,2-trifluoroe
  • R 6 in Formula [5] represents a hydrocarbyl group or a halogenated hydrocarbyl group.
  • the hydrocarbyl group in R 6 is preferably an alkyl group, an aryl group or an aralkyl group, and the same hydrocarbyl group as that described as L 2 in Formula [5] is used. Examples of the
  • halogenated hydrocarbyl group in R 6 include a halogenated alkyl group, a halogenated aryl group, a (halogenated alkyl)aryl group and the like, and the same halogenated alkyl group, halogenated aryl group and (halogenated alkyl)aryl group as those listed as examples of the electron withdrawing group in R 5 of Formula [4] are used.
  • R 6 in Formula [5] is preferably a halogenated hydrocarbyl group, and more preferably a fluorinated hydrocarbyl group.
  • Examples of the compound (a) to be used to obtain the modified particles (I) include, when M 3 is a zinc atom, dialkyl zinc such as dimethyl zinc, diethyl zinc, dipropyl zinc, di-n-butyl zinc, diisobutyl zinc or di-n-hexyl zinc; diaryl zinc such as diphenyl zinc, dinaphthyl zinc or
  • bis(pentafluorophenyl)zinC) ' dialkenyl zinc such as diallyl zinc! halogenated alkyl zinc such as bis(cyclopentadienyl) zinc, methyl zinc chloride, ethyl zinc chloride, propyl zinc chloride, n-butyl zinc chloride, isobutyl zinc chloride, n- hexyl zinc chloride, methyl zinc bromide, ethyl zinc bromide, propyl zinc bromide, n-butyl zinc bromide, isobutyl zinc bromide, n-hexyl zinc bromide, methyl zinc iodide, ethyl zinc iodide, propyl zinc iodide, n-butyl zinc iodide, isobutyl zinc iodide or n-hexyl zinc iodide; and halogenated zinc such as zinc fluoride, zinc chloride, zinc bromide
  • the compound (a) is preferably dialkyl zinc, more preferably dimethyl zinc, diethyl zinc, dipropyl zinc, di-n-butyl zinc, diisobutyl zinc or di-n-hexyl zinc, and particularly preferably dimethyl zinc or diethyl zinc.
  • Examples of the amines of the compound (b) include
  • Examples of the alcohols of the compound (b) include fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol,
  • thiol compounds in which an oxygen atom is substituted with a sulfur atom.
  • Those thiol compounds are compounds in which methanol of the above examples is replaced by methanethiol, ethanol is replaced by ethanethiol, and propanol is replaced by propanethiol.
  • Examples of the phenols of the compound (b) include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,4-difluorophenol, 2,6-difluorophenol, 3,4- difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5- trifluorophenol, 2,3,5,6-tetrafluorophenol, pentafluorophenol, 2,3,5,6- tetrafluoro-4-trifluoromethylphenol, 2,3,5,6-tetrafluoro-4- pentafluorophenylphenol, perfluoro-l-naphthol, perfluoro-2-naphthol, 2- chlorophenol, 3-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,6- dichlorophenol, 3,4-dichlorophenol, 3,5-dichlorophenol, 2,4,6-trichlorophenol, 3,4,5-trichlorophenol, 2,3,5,
  • pentabromophenol 2,3,5,6-tetrabromo-4-tribromomethylphenol, 2,3,5,6- tetrabromo-4-pentabromophenylphenol, perbromo-l-naphthol, perbromo-2- naphthol, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2,4-diiodophenol, 2,6- diiodophenol, 3,4-diiodophenol, 3,5-diiodophenol, 2,4,6-triiodophenol, 3,4,5- triiodophenol, 2,3,5,6-tetraiodophenol, pentaiodophenol, 2,3,5,6"tetraiodo-4- triiodomethylphenol, 2,3,5,6-tetraiodo-4-pentaiodophenylphenol, periodo-1- naphthol, periodo-2-naphthol, 2-(trifluoro
  • thiophenol compounds are compounds in which phenol of the above examples is replaced by thiophenol.
  • the amine of the compound (b) is
  • bis(trifluoromethyl)amine bis(2,2,2-trifluoroethyl)amine, bis(2, 2,3,3,3- pentafluoropropy amine, bis(2,2,2-trifluoro-l-trifluoromethylethyl)amine, bis(l,l-bis(trifluoromet yl)-2,2,2-trifluoroethyl)amine or
  • the phenol of the compound (b) is 2-fluorophenol, 3- fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6- trifluorophenol, 3,4,5-trifluorophenol, pentafluorophenol, 2- (trifluoromethyl)phenol, 3-(trifluoromethyl)phenol, 4- (trifluoromethyDphenol, 2,6-bis(trifluoromethyl)phenol, 3,5- bis(trifluoromethyl)phenol, 2,4,6-tris(trifluoromethyl)phenol or 3,4,5- tris (trifluoromethy l)p he nol .
  • the compound (b) is more preferably bis(trifluoromethyl)amine, bis(pentafluorophenyl)amine, trifluoromethanol, 2,2,2-trifluoro-l- trifluoromethylethanol, 1, l-bis(trifluoromethyl)-2,2,2-trifluoroethanol, 2- fluorophenol, 3-fluorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5- difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol,
  • pentafluorophenol 4-(trifluoromethyl)phenol, 2,6-bis(trifluoromethyl)phenol or 2,4,6-tris(trifluoromethyl)phenol, and still more preferably 3,5- difluorophenol, 3,4,5-trifluorophenol, pentafluorophenol or 1,1- bis(trifluoromethyl) -2,2, 2 - trifluoroethanol.
  • Examples of the compound (c) include water, hydrogen sulfide, amine and an aniline compound.
  • Examples of the amine include
  • alkylamines such as methylamine, ethylamine, n-propylamine, isopropylamine, rrbutylamine, sec-butylamine, tert-butylamine,
  • difluoromethy lamine trifluoromethylamine , 2, 2, 2 -trifluoroethylamine , 2,2,3,3,3-pentafluoropropylamine, 2,2,2-trifluoro-l- trifluoromethylethy lamine , 1,1 -bis(trifluoromethyl) -2,2,2- trifluoroethylamine, perfluoropropylamine, perfluorobutylamine,
  • perfluoropentylamine perfluorohexylamine, perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine; and halogenated alkylamines in which "fluoro" of these amines are replaced by "chloro", “bromo” or "iodo".
  • aniline compound of the compound (c) examples include aniline, naphthylamine, anthraceny lamine, 2-tolylamine, 3-tolylamine, 4- toly lamine, 2,3-xylylamine, 2,4-xylylamine, 2,5-xylylamine, 2,6-xylylamine, 3,4-xylylamine, 3,5-xylylamine, 2,3,4-trimethylaniline, 2,3,5- trimethylaniline, 2,3,6-trimethylaniline, 2,4,6-trimethylaniline, 3,4,5- trimethylaniline , 2,3,4, 5 - tetr amethylaniline , 2,3,4, 6 - tetramethylaniline , 2,3,5,6-tetramethylaniline, pentamethylaniline, 2 -ethylaniline, 3- ethylaniline, 4-ethylaniline, 2,3-diethylaniline, 2,4-diethylaniline, 2,5- diethylaniline
  • the compound (c) is preferably water, hydrogen sulfide,
  • perfluorooctylamine perfluoropentadecylamine
  • 2 -fluoroaniline 3- fluoroaniline
  • 4-fluoroaniline 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6- trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3-(trifluoromethyl)aniline, 4-
  • Examples of (d) include inorganic oxide particles and organic polymer particles. Among them, porous particles having a uniform particle diameter, which are commonly used as a carrier, are preferable. From the viewpoint of the particle size distribution of the obtained addition polymer, regarding the particle size distribution of (d), the vobame based geometric standard deviation of the particle diameter of (d) is preferably 2.5 or less, more preferably 2.0 or less, and still more preferably 1.7 or less.
  • any inorganic oxide or a mixture of any inorganic oxide may be used as the inorganic oxide particles of (d).
  • the inorganic oxide include Si0 2 , A1 2 0 3 , MgO, ZrO 2 , TiO 2) B 2 0 3 , CaO, ZnO, BaO, and Th0 2 , and a mixture thereof, Si0 2 -MgO, SiO 2 -Al 2 0 3 , SiO 2 -Ti0 2) SiO 2 -V 2 O 5 , SiO 2 -Cr 2 O 3 , and Si0 2 -Ti0 2 -MgO.
  • These inorganic oxides are preferably Si0 2 and/or A1 2 0 3 , and particularly preferably Si0 2 (i.e., silica).
  • the above inorganic oxide may contain a small amount of carbonates, sulfates, nitrates, and oxide components, such as Na 2 C0 3 , K 2 C0 3 , CaCO 3 , MgCO 3 , Na 2 SO 4 , A1 2 (S0 4 ) 3 , BaS0 4 , KN0 3 , Mg(NO 3 ) 2 , A1(N0 3 )3, Na 2 O, K 2 O, and Li 2 O.
  • the inorganic oxide is preferably dried to substantially remove moisture, and a drying method is preferably a method of drying by heating.
  • the drying temperature is usually a temperature within a range from 100 to 1,500°C, preferably from 100 to 1,000°C, and still more preferably from 200 to 800°C, for the inorganic oxide in which moisture cannot be visually confirmed.
  • There is no particular limitation on the drying time and it is preferably from 10 minutes to 50 hours, and more preferably from 1 hour to 30 hours.
  • Examples of the method of drying by heating include a method in which drying is carried out by circulating a dried inert gas (for example, nitrogen or argon, etc.) at a given flow rate during heating, or a method in which drying is carried out by heating under reduced pressure.
  • hydroxyl groups are formed and present on the surface of an inorganic oxide.
  • a modified inorganic oxide produced by substituting active hydrogen of surface hydroxyl groups with various substituents may be used as the inorganic oxide.
  • Examples of the modified inorganic oxide include inorganic oxides subjected to a contact treatment with
  • trialkylchlorosilane such as trimethylchlorosilane or tert- butyldimethylchlorosilanei triarylchlorosilane such as triphenylchlorosilane; dialkyldichlorosilane such as dimethyldichlorosilane, ' diaryldichlorosilane such as diphenyldichlorosilane; alkyltrichlorosilane such as
  • aryltrichlorosilane such as phenyltrichlorosilane; trialkylalkoxysilane such as trimethylmethoxysilane; triarylalkoxysilane such as tri henylmethoxysilane; dialkyldialkoxysilane such as
  • diaryldialkoxysilane such as
  • methyltrimethoxysilane methyltrimethoxysilane
  • aryltrialkoxysilane such as
  • phenyltrimethoxysilane tetraalkoxysilane such as tetramethoxysilane
  • alkyldisilazane such as 1, 1,1,3,3,3-hexamethyldisilazane
  • tetrachlorosilane alcohol such as methanol or ethanol
  • alcohol such as methanol or ethanol
  • dialkyl magnesium such as dibutyl magnesium, butylethyl magnesium or butyloctyl magnesium
  • alkyl lithium such as butyl lithium.
  • Further examples include inorganic oxides produced by subjecting inorganic oxides which have brought into contact with trialkyl aluminum to a contact treatment with dialkylamine such as diethylamine or
  • diphenylamine diphenylamine
  • alcohol such as methanol or ethanol
  • phenol phenol
  • the strength of the inorganic oxide per se may be sometimes increased by the hydrogen bond of hydroxyl groups to each other. In that case, if all active hydrogens of surface hydroxyl groups are substituted with various substituents, a decrease in particle strength may sometimes occur. Therefore, it is not necessarily required to substitute all active hydrogens of surface hydroxyl groups of the inorganic oxide, and the substitution rate of the surface hydroxyl group may be appropriately determined. There is no particular limitation on a method of changing the substitution rate of the surface hydroxyl group. Examples of the method include a method of changing the amount of the compound to be used in the contact treatment. [0153]
  • the average particle diameter of inorganic oxide particles is usually from 1 to 5,000 pm, preferably from 5 to 1,000 pm, more preferably from 10 to 500 pm, and still more preferably from 10 to 100 pm.
  • the pore volume is preferably 0.1 ml/g or more, and more preferably from 0.3 to 10 ml/g.
  • the specific surface area is preferably from 10 to 1,000 m 2 /g, and more
  • organic polymer particles (d) Any organic polymer or a mixture of any organic polymer may be used as the organic polymer particles (d).
  • the organic polymer is
  • a polymer which has a functional group containing active hydrogen, or a non-proton-donating Lewis basic functional group.
  • Examples of the functional group include a primary amino group, a secondary amino group, an imino group, an amide group, a hydrazide group, an amidino group, a hydroxy group, a hydroperoxy group, a carboxyl group, a formyl group, a carbamoyl group, a sulfonic acid group, a sulfinic acid group, a sulfenic acid group, a thiol group, a thioformyl group, a pyrrolyl group, an imidazolyl group, a piperidyl group, an indazolyl group and a carbazolyl group.
  • the functional group is preferably a primary amino group, a secondary amino group, an imino group, an amide group, an imide group, a hydroxy group, a formyl group, a carboxyl group, a sulfonic acid group or a thiol group, and particularly preferably a primary amino group, a secondary amino group, an amide group or a hydroxy group.
  • These groups may be substituted with a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms.
  • the non-proton-donating Lewis basic functional group is a functional group which has a Lewis basic moiety having no active hydrogen atom.
  • the functional group include a pyridyl group, an N-substituted imidazolyl group, an N- substituted indazolyl group, a nitrile group, an azide group, an N- substituted imino group, an ⁇ , ⁇ -substituted amino group, an N,N- substituted aminooxy group, an ⁇ , ⁇ , ⁇ -substituted hydrazino group, a nitroso group, a nitro group, a nitrooxy group, a furyl group, a carbonyl group, a thiocarbonyl group, an alkoxy group, an alkyloxycarbonyl group, an ⁇ , ⁇ -substituted carbamoyl group, a thioalkoxy group, a substituted sulfinyl group
  • the functional group is preferably a heterocyclic group, and more preferably an aromatic heterocyclic group having an oxygen atom and/or a nitrogen atom in the ring.
  • the functional group is particularly preferably a pyridyl group, an N-substituted imidazolyl group, or an N-substituted indazolyl group, and most preferably a pyridyl group. These groups may be substituted with a halogen atom, or a hydrocarbyl group having 1 to 20 carbon atoms.
  • the content of the functional group having active hydrogen or non-proton-donating Lewis basic functional group in the organic polymer is preferably from 0.01 to 50 mmol/g, and more preferably from 0.1 to 20 mmol/g, expressed by a molar amount of a functional group per gram of the organic polymer.
  • Examples of a method for producing the organic polymer, which has a functional group having active hydrogen or a non-proton-donating Lewis basic functional group include a method of homopolymerizing a monomer which has a functional group having active hydrogen or a non-proton- donating Lewis basic functional group, and one or more polymerizable unsaturated groups, or a method of copolymerizing the said monomer with the other monomer having a polymerizable unsaturated group. It is preferred to copolymerize together with a crosslinking polymerizable monomer having two or more polymerizable unsaturated groups at this time.
  • Examples of the polymerizable unsaturated group include alkenyl groups such as a vinyl group and an allyl group; and alkynyl groups such as an ethyne group.
  • Examples of the monomer which has a functional group having active hydrogen and one or more polymerizable unsaturated groups include a vinyl group -containing primary amine, a vinyl grou -containing secondary amine, a vinyl group -containing amide compound, and a vinyl group -containing hydroxy compound.
  • Examples of the monomer include N- (l-ethenyl)amine, N-(2-propenyl)amine, N-(l-ethenyl)-N-methylamine, N-(2- propenyl)-N-methylamine, 1-ethenylamide, 2-propenylamide, N-methyHl- ethenyl) amide, N-methyl-(2-propenyl)amide, vinyl alcohol, 2-propen-l-ol, and 3-buten-l"ol.
  • Examples of the monomer which has a functional group having a Lewis basic moiety with no active hydrogen atom and one or more polymerizable unsaturated groups include vinylpyridine, vinyl(N- substituted) imidazole, and vinyl(N-substituted) indazole.
  • Examples of the other monomer having a polymerizable unsaturated group include ethylene, crolefin, an aromatic vinyl compound and a cyclic olefin compound.
  • Examples of the monomer include ethylene, propylene, 1; butene, 1-hexene, 4-methyM-pentene, styrene, norbornene and
  • dicyclopentadiene Ethylene or styrene is preferred. Two or more kinds of these monomers may be used.
  • crosslinking polymerizable monomer having two or more polymerizable unsaturated groups include divinylbenzene and the like.
  • the average particle diameter of the organic polymer particles is usually from 1 to 5,000 ⁇ , preferably from 5 to 1,000 pm, and more preferably from 10 to 500 pm.
  • the pore volume is preferably 0.1 ml/g or more, and more preferably 0.3 to 10 ml/g.
  • the specific surface area is preferably from 10 to 1,000 m 2 /g, and more preferably from 50 to 500 m lg.
  • These organic polymer particles are preferably dried to substantially remove moisture, and more preferably dried by heating.
  • the drying temperature of the organic polymer whose moisture cannot be visually confirmed is usually from 30 to 400°C, preferably from 50 to 200°C, and more preferably from 70 to 150°C.
  • Examples of the method of drying the organic polymer particles by heating include a method in which organic polymer particles are dried by circulating a dried inert gas (e.g., nitrogen, argon, etc.) at a given flow rate while heating, or a method in which organic polymer particles are dried by heating under reduced pressure.
  • a dried inert gas e.g., nitrogen, argon, etc.
  • ⁇ 1> an order in which a contact product of (a) and (b) is brought into contact with (c) to obtain a contact product and the obtained contact product is brought into contact with (d);
  • ⁇ 2> an order in which a contact product of (a) and (b) is brought into contact with (d) to obtain a contact product and the obtained contact product is brought into contact with (c);
  • ⁇ 3> an order in which a contact product of (a) and (c) is brought into contact with (b) to obtain a contact product and the obtained contact product is brought into contact with (d);
  • ⁇ 5> an order in which a contact product of (a) and (d) is brought into contact with (b) to obtain a contact product and the obtained contact product is brought into contact with (c);
  • ⁇ 6> an order in which a contact product of (a) and (d) is brought into contact with (c) to obtain a contact product and the obtained contact product is brought into contact with (b);
  • ⁇ 7> an order in which a contact product of (b) and (c) is brought into contact with (a) to obtain a contact product and the obtained contact product is brought into contact with (d);
  • ⁇ 8> an order in which a contact product of (b) and (c) is brought into contact with (d) to obtain a contact product and the obtained contact product is brought into contact with (a);
  • ⁇ 11> an order in which a contact product of (c) and (d) is brought into contact with (a) to obtain a contact product and the obtained contact product is brought into contact with (b);
  • ⁇ 12> an order in which a contact product of (c) and (d) is brought into contact with (b) to obtain a contact product and the obtained contact product is brought into contact with (a).
  • the contact order is preferably ⁇ 1>, ⁇ 2>, ⁇ 3>, ⁇ 5>, ⁇ 11> or ⁇ 12> described above.
  • the contact order is particularly preferably ⁇ 2> or ⁇ 5>.
  • Such a contact treatment is preferably carried out under an inert gas atmosphere.
  • the treatment temperature is usually from -100 to 300°C, and preferably from -80 to 200°C.
  • the treatment time is usually from 1 minute to 200 hours, and preferably from 10 minutes to 100 hours.
  • Such a treatment may be carried out using a solvent, or these compounds may be directly brought into contact with each other without using a solvent.
  • a solvent which is inert to (a), (b), (c), (d) described above and contact products thereof is used as the solvent.
  • a solvent capable of reacting with a certain compound in a certain stage can be used in another stage if the solvent does not react with each compound in another stage. That is, the solvent to be used in each step is the same or different.
  • the solvent examples include nonpolar solvents such as an aliphatic hydrocarbyl solvent and an aromatic hydrocarbyl solvent; and polar solvents such as a halide solvent, an ether- based solvent, an alcohol-based solvent, a phenol-based solvent, a carbonyl- based solvent, a phosphoric acid derivative, a nitrile -based solvent, a nitro compound, an amine -based solvent and a sulfur compound.
  • nonpolar solvents such as an aliphatic hydrocarbyl solvent and an aromatic hydrocarbyl solvent
  • polar solvents such as a halide solvent, an ether- based solvent, an alcohol-based solvent, a phenol-based solvent, a carbonyl- based solvent, a phosphoric acid derivative, a nitrile -based solvent, a nitro compound, an amine -based solvent and a sulfur compound.
  • Examples thereof include aliphatic hydrocarbyl solvents such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane and cyclohexane; aromatic hydrocarbyl solvents such as benzene, toluene and xylene!
  • halide solvents such as dichloromethane, difluoromethane, chloroform, 1,2-dichloroethane, 1,2- dibromoethane , 1, 1, 2 - trichloro- 1,2,2 -trifluoroethane , tetr achloroethylene , chlorobenzene, bromobenzene and o-dichlorobenzene; ether-based solvents such as dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl-ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis(2- methoxyethy ether, tetrahydrofuran and tetrahydropyran, ' alcohol-based solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2- butanol, 2-methyl- 1-
  • propionitrile succinonitrile and benzonitrile
  • nitro compounds such as riitromethane and nitrobenzene!
  • amine-based solvents such as pyridine, piperidine and morpholine!
  • sulfur compounds such as dimethyl sulfoxide and sulfolane.
  • a solvent (si) is preferably the above aliphatic hydrocarbyl solvent, aromatic hydrocarbyl solvent or ether-based solvent.
  • a solvent (s2) is preferably a polar solvent.
  • the ⁇ ⁇ value (C. Reichardt, "Solvents and Solvents Effects in Organic Chemistry", 2nd ed., VCH Verlag (1988)) or the like is known as an indicator which represents the polarity of the solvent, and a solvent satisfying the range of the following inequality expression: 0.8 > ⁇ ⁇ > 0.1 is particularly preferred.
  • the polar solvent include dichloromethane,
  • dichlorodifluoromethanechloroform 1,2- dichloroethane , 1,2- dibromoethane , 1, 1,2-trichloro- 1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, o-dichlorobenzene, dimethyl ether, diethyl ether, diisopropyl ether, drn-butyl ether, methyHert-butyl ether, anisole, 1,4-dioxane, 1,2- dimethoxy ethane, bis(2-methoxyethyl)ether, tetrahydrofuran,
  • tetrahydropyran methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2- butanol, 2-methyl- 1-propanol, 3 -methyl- 1-butanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2- ethoxyethanol, diethylene glycol, triethylene glycol, acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, ⁇ , ⁇ -dimethylformamide, N,N- dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric acid triamide, triethyl phosphate, acetonitrile, propionitrile, succinonitrile, benzonitrile, nitromethane, nitrobenzene,
  • the solvent (s2) is more preferably dimethyl ether, diethyl ether, diisopropyl ether, di-n- butyl ether, methyl -tert- butyl ether, anisole, 1,4-dioxane, 1,2- dimethoxyethane, bis(2-methoxyethyl)ether, tetrahydrofuran,
  • tetrahydropyran methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2- butanol, 2-methyl- 1-propanol, 3-methyl- l-butanol, cyclohexanol,
  • benzylalcohol ethylene glycol, propylene glycol, 2-methoxyethanol, 2- ethoxyethanol, diethylene glycol or triethylene glycol, particularly
  • tetrahydrofuran methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2- butanol, 2-methyl-l-propanol, 3-methyl-l-butanol or cyclohexanol, and most preferably tetrahydrofuran, methanol, ethanol, 1-propanol or 2-propanol.
  • solvent (s2) a mixed solvent of the polar solvent and a hydrocarbyl solvent.
  • the aliphatic hydrocarbyl solvent and the aromatic hydrocarbyl solvent listed above are used as the solvent (s2)
  • Examples of the mixed solvent of the polar solvent and the hydrocarbyl solvent can include a hexane/methanol mixed solvent, a hexane/ethanol mixed solvent, a hexane/l-propanol mixed solvent, a hexane/2-propanol mixed solvent, a heptane/methanol mixed solvent, a heptane/ethanol mixed solvent, a heptane/l-propanol mixed solvent, a heptane/2-propanol mixed solvent, a toluene/methanol mixed solvent, a toluene/ethanol mixed solvent, a toluene/ 1-propanol mixed solvent, a toluene/2-propanol mixed solvent, a xylene/methanol mixed solvent, a xylene/ethanol mixed solvent, a xylene/1 -propanol mixed solvent and a xylene/2-propanol mixed solvent.
  • the mixed solvent is preferably a hexane/methanol mixed solvent, a hexane/ethanol mixed solvent, a heptane/methanol mixed solvent, a heptane/ethanol mixed solvent, a toluene/methanol mixed solvent, a toluene/ethanol mixed solvent, a xylene/methanol mixed solvent or a xylene/ethanol mixed solvent.
  • the mixed solvent is more preferably a hexane/methanol mixed solvent, a hexane/ethanol mixed solvent, a toluene/methanol mixed solvent or a toluene/ethanol mixed solvent.
  • the mixed solvent is most preferably a toluene/ethanol mixed solvent.
  • the content of an ethanol fraction in the toluene/ethanol mixed solvent is preferably within a range from 10 to 50% by volume, and more preferably from 15 to 30% by volume.
  • a hydrocarbyl solvent as the solvent (si) and the solvent (s2) in a method in which the contact product (f) produced by bringing (a), (b) and (c) into contact with each other is brought into contact with (d), namely, in the respective methods of ⁇ 1>, ⁇ 3> and ⁇ 7> described above.
  • the time is preferably from 0 to 5 hours, more preferably from 0 to 3 hours, and most preferably from 0 to 1 hour.
  • the temperature at that time is usually from - 100°C to 40°C, preferably from -20°C to 20°C, and most preferably from - 10°C to 10°C.
  • any of the above nonpolar solvent and the above polar solvent can be used.
  • the nonpolar solvent is preferred. The reason is considered that, since a contact product of (a) and (c), or a contact product produced by bringing a contact product of (a) and (b) into contact with (c) commonly exhibits low solubility in a nonpolar solvent, in a case where (d) exists in a reaction system when these contact products are formed, the thus formed contact products are precipitated on a surface of (d) and are more likely to be immobilized.
  • m in Formula (l) represents the valence of M 3 .
  • y in Formula (l) is preferably a number of 0.01 to 1.99, more preferably a number of 0.10 to 1.80, still more preferably a number of 0.20 to 1.50, and most preferably a number of 0.30 to 1.00.
  • Preferable range of z in Formula (l) is determined by m, y and Formula (l).
  • Compounds (a) and (d) are each used in such an amount that the number of typical metal atoms derived from the compound (a) contained in the modified particles (I) is preferably 0.05 mmol or more, and more preferably from 0.1 to 20 mmol, expressed by the molar number of the typical metal atoms per gram of the produced modified particles (I).
  • a heating step at a higher temperature is preferably added after the contact treatment described above.
  • a solvent having a high boiling point is preferably used so as to achieve a higher temperature.
  • the solvent used in the contacting step may be replaced by another solvent having a higher boiling point.
  • the compounds (a), (b), (c) and/or (d) as raw materials may remain as an unreacted product.
  • the produced modified particles (I) are preferably washed so as to remove the unreacted product from the produced modified particles (I).
  • a solvent to be used to wash the modified particles (I) may be the same or different used to produce the modified particles (I).
  • the modified particles (I) are preferably washed under an inert gas atmosphere.
  • the washing temperature is usually from - 100 to 300°C, and preferably from -80 to 200°C.
  • the washing time is usually from 1 minute to 200 hours, and preferably from 10 minutes to 100 hours.
  • modified particles (I) in the solvent are sedimented and amorphous or fine particles adjufloat at the upper portion of slurry, in the case of the above washing treatment, so as to obtain modified particles (I) having a uniform particle diameter and shape.
  • the solvent is preferably distilled off from the product, followed by drying the product at a temperature of 0°C or higher under reduced pressure for 1 hour to 24 hours.
  • the drying treatment is more preferably carried out at a temperature of 0°C to 200°C for 1 hour to 24 hours, still more preferably at a temperature of 10°C to 200°C for 1 hour to 24 hours, particularly preferably at a
  • Examples of a method for producing the modified particles (I) is described in more detail below by way of a case where M 3 is a zinc atom, the compound (b) is 3,4,5-trifluorophenol, the compound (c) is water, and (d) is silica.
  • M 3 is a zinc atom
  • the compound (b) is 3,4,5-trifluorophenol
  • the compound (c) is water
  • (d) is silica.
  • tetrahydrofuran as a solvent
  • a solution of diethyl zinc in hexane is added thereto to form a mixture (l).
  • 3,4,5-trifluorophenol is added dropwise to the mixture (l) in an equimolar amount based on the amount of diethyl zinc to form a mixture (2), followed by stirring the mixture (2) at room temperature for 10 minutes to 24 hours.
  • water is added dropwise to the mixture (2) in a
  • a cyclic aluminoxane having a structure represented by Formula ⁇ ⁇ Al(E 2 )-0- ⁇ e and/or a linear aluminoxane having a structure represented by Formula E 3 ⁇ -Al(E 3 )-0- ⁇ cAlE 3 2 is/are preferably used as the aluminoxane (e) used in the preparation of modified particles (II).
  • E 2 and E 3 each represent a hydrocarbyl group, each E 2 may be the same or different, each E 3 may be the same or different, e represents a number of 2 or more, and c represents a number of 1 or more.
  • the hydrocarbyl group in E 2 or E 3 is preferably a hydrocarbyl group having 1 to 8 carbon atoms, and more preferably an alkyl group.
  • E 2 and E 3 include alkyl groups such as a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a normal pentyl group and a neopentyl group, e is a number of 2 or more, and c is a number of 1 or more.
  • E 2 and E 3 are preferably methyl groups or isobutyl groups, e is from 2 to 40, and c is from 1 to 40.
  • the above aluminoxane can be produced by various methods.
  • the aluminoxane may be produced in accordance with a known method.
  • the aluminoxane can be produced by bringing a solution, prepared by dissolving trialkyl aluminum (e.g., trimethyl aluminum, etc.) in a proper organic solvent (benzene, aliphatic hydrocarbyl, etc.), into contact with water.
  • trialkyl aluminum e.g., trimethyl aluminum, etc.
  • organic solvent benzene, aliphatic hydrocarbyl, etc.
  • the method include a method in which the aluminoxane is produced by bringing a metal salt containing crystal water (e.g., copper sulfate hydrate, etc.) into contact with trialkyl aluminum (e.g., trimethyl aluminum, etc.). It is considered that the aluminoxane produced by such a method is usually a mixture of a cyclic aluminoxane and a linear
  • the particles (d) used to obtain the modified particles (II) are particles similar to (d) used in the modified particles (I).
  • the modified particles (II) can be produced by bringing the
  • the modified particles (II) can be produced by dispersing the particles (d) in a solvent and adding the aluminoxane (e) thereto.
  • any solvent described in the description of the method for producing the modified particles (I) can be used, and the solvent is preferably a solvent which does not react with the aluminoxane (e), and more preferably a solvent which dissolves the aluminoxane (e).
  • aromatic hydrocarbyl solvents such as toluene and xylene, or aliphatic hydrocarbyl solvents such as hexane, heptane and octane are preferred, and toluene or xylene is more preferred.
  • the contacting temperature and contacting time used in the case of bringing the aluminoxane (e) into contact with the particles (d) can be optionally selected.
  • the temperature is usually from -100°C to 200°C, preferably from -50°C to 150°C, and still more preferably from -20°C to
  • the amounts of the aluminoxane (e) and the particles (d), which are brought into contact with each other, are optional amounts.
  • the amount of the aluminoxane (e) is usually from 0.01 to 100 mmol, preferably from 0.1 to 20 mmol, and still more preferably from 1 to 10 mmol, expressed by aluminum atoms per gram of the particles (d).
  • Modified particles (III) are produced by further using the compound (A) in the preparation of the modified particles (II).
  • transition metal compound represented by Formula [4] or its ⁇ - oxo type transition metal compound dimer is used as the compound (A).
  • the modified particles (III) can be produced by brining the pulp
  • aluminoxane (e), the particles (d) and the compound (A) into contact with each other using any method. It is preferable that the aluminoxane (e), the particles (d) and the compound (A) be brought into contact with each other in a solvent. It is also possible to use, as the solvent, any solvent described above.
  • the solvent is preferably a solvent which does not react with the aluminoxane (e) and the compound (A), and more preferably a solvent which dissolves the aluminoxane (e) and the compound (A).
  • aromatic hydrocarbyl solvents such as toluene and xylene, or aliphatic hydrocarbyl solvents such as hexane, heptane and octane are preferred, and toluene or xylene is more preferred.
  • the contacting temperature and contacting time used in the case of bringing the aluminoxane (e), the particles (d) and the compound (A) into contact with each other are optionally selected.
  • the temperature is usually from - 100°C to 200°C, preferably from -50°C to 150°C, and still more preferably from -20°C to 120°C. Particularly in an initial stage of the reaction, these are preferably reacted at a low temperature so as to suppress heat generation.
  • the amounts of the aluminoxane (e), the particles (d) and the compound (A), which are brought into contact with each other, are optional amounts.
  • the amount of the aluminoxane (e) is usually from 0.01 to 100 mmol, preferably from 0.1 to 20 mmol, and still more preferably from 1 to 10 mmol, expressed by aluminum atoms per gram of the particles (d).
  • the amount of the compound (A) is usually from 0.1 to 1,000 pmol,
  • the organoalminium compound (C) to be used in the present invention is a known organoalminium compound. It is preferably an organoalminium compound represented by Formula [8] :
  • each R 9 independetly represents a hydrocarbyl group
  • each Y independetly represents a hydrogen atom, a halogen atom, an alkoxy group, an aralkyloxy group or an aryloxy group
  • d is a number satisfying 0 ⁇ d ⁇ 3.
  • R 9 in Formula [8] is preferably a hydrocarbyl group having 1 to 24 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms.
  • R6 include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, an isobutyl group, a n-hexyl group, a 2-methylhexyl group, a n-octyl group and the like, and preferably an ethyl group, a n-butyl group, an isobutyl group, a n-hexyl group or a n-octyl group.
  • Examples of a case where Y is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and preferably a chlorine atom.
  • the alkoxy group in Y is preferably an alkoxy group having 1 to 24 carbon atoms, and examples of the aokoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentoxy group, a neopentoxy group, a n-hexoxy group, a n-octoxy group, a n-dodesoxy group, a n- pentadesoxy group, a n-icosoxy group and the like, and preferably a methoxy group, an ethoxy group or a tert-butoxy group.
  • the aryloxy group in Y is preferably an aryloxy group having 6 to 24 carbon atoms, and examples of the aryloxy group include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2,3-dimethylphenoxy group, a 2,4-dimethylphenoxy group, a 2,5" dimethylphenoxy group, a 2,6-dimethylphenoxy group, a 3,4- dimethylphenoxy group, a 3,5-dimethylphenoxy group, a 2,3,4- trimethylphenoxy group, a 2,3,5-trimethylphenoxy group, a 2,3,6- trimethylphenoxy group, a 2,4,5-trimethylphenoxy group, a 2,4,6- trimethylphenoxy group, a 3,4,5-trimethylphenoxy group, a 2,3,4,5- tetramethylphenoxy group, a 2, 3, 4, 6 -tetramethylphenoxy group, a 2,3,5,6- tetramethylphenoxy group,
  • the aralkyloxy group in Y is preferably an aralkyloxy group having 7 to 24 carbon atoms, and examples ot the aralkyloxy group include a benzyloxy group, a (2-methylphenyl)methoxy group, a (3- methylphenyDmethoxy group, a (4-methylphenyl)methoxy group, a (2,3- dimethylphenyDmethoxy group, a (2,4"dimethylphenyl)methoxy group, a (2,5-dimethylphenyl)methoxy group, a (2,6-dimethylphenyl)methoxy group, a (3,4-dimethylphenyl)methoxy group, a (3,5-dimethylphenyl)methoxy group, a (2,3,4-trimethylphenyDmethoxy group, a (2,3,5-trimethylphenyl)methoxy group, a (2,3,6-trimethylphenyl)methoxy group,
  • anthracenylmethoxy group and the like and the like, and preferably a benzyloxy group.
  • Formula [8] include trialkyl aluminums such as trimethyl aluminum, triethyl aluminum, trrn-propyl aluminum, trrn-butyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum and tri-n-octyl aluminum; dialkyl aluminum chlorides such as dimethyl aluminum chloride, diethyl aluminum chloride, di-n-propyl aluminum chloride, di-n-butyl aluminum chloride, diisobutyl aluminum chloride and di-n-hexyl aluminum chloride; alkyl aluminum dichlorides such as methyl aluminum dichloride, ethyl aluminum dichloride, n-propyl aluminum dichloride, n-butyl aluminum dichloride, isobutyl aluminum dichloride and n-hexyl aluminum dichloride; dialkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl
  • alkyl(dialkoxy) aluminums such as methyl(dimethoxy) aluminum
  • dialkyl (alkoxy) aluminums such as dimethyl(methoxy) aluminum, dimethyl(ethoxy) aluminum and dimethyl(tert-butoxy) aluminum;
  • alkyl(diaryloxy) aluminums such as methyl(diphenoxy) aluminum, methylbis(2,6-diisopropylphenoxy) aluminum and methylbis(2,6- diphenylphenoxy) aluminum; and dialkyl(aryloxy) aluminums such as dimethyl(phenqxy) aluminum, dimethyl(2,6-diisopropylphenoxy) aluminum and dimethyl(2,6-diphenylphenoxy) aluminum.
  • the organoaluminum compound is preferably trialkyl aluminum, more preferably trimethyl aluminum, triethyl aluminum, tri-n- butyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum or tri-n-octyl aluminum, and particularly preferably triisobutyl aluminum or tri-n-octyl aluminum.
  • organoaluminum compounds may be used alone, or two or more kinds of them may be used in combination.
  • an electron-donating compound (E) may be brought into contact with a catalyst or a prepolymerized catalyst component for addition polymerization.
  • the electron- donating compound (E) is preferably a compound containing a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom, and examples thereof include an oxygen-containing compound, a nitrogen- containing compound, a phosphorus-containing compound, and a sulfur- containing compound, and among them, an oxygen-containing compound or a nitrogen-containin compound is preferabe.
  • oxygen- containing compound examples include alkoxysilicons, ethers, ketones, aldehydes, carboxylic acids, esters of organic acid or inorganic acid, acid amides of organic acid or inorganic acid, acid anhydrides and the like, and among them, alkoxysilicons or ethers are preferable.
  • nitrogen- containing compound examples include amines, nitriles, isocyanates and the like, and amines are preferable.
  • the alkoxysilicon is preferably an alkoxysilane represented by
  • each R 10 independently represents a hydrocarbyl group having 1 to 20 carbon atoms, a hydrogen atom, or a hetero atom-containing substituent! each R 11 independently represents a hydrocarbyl group having 1 to 20 carbon atoms; r represents a number satisfying 0 ⁇ r ⁇ 4.
  • R 10 and R 11 are hydrocarbyl groups
  • examples thereof include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group; branched alkyl groups such as an isopropyl group, a sec-butyl group, a tert-butyl group, and a tert-amyl group;
  • cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group
  • R 10 is a hetero atom - containing substituent
  • examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.
  • Examples thereof include a dimethylamino group, a methylethylamino group, a diethylamino group, an ethyl-n-propylamino group, a di-n-propylamino group, a pyrrolyl group, a pyridyl group, a pyrrolidinyl group, a piperidyl group, a
  • perhydroindolyl group a perhydroisoindolyl group, a perhydroquinolyl group, a perhydroisoquinolyl group, a perhydrocarbazolyl group, a
  • perhydroacridinyl group a furyl group, a pyranyl group, a perhydrofuryl group, a thienyl group and the like.
  • R 10 and R 11 are preferably alkyl groups, and also r is preferably a number satisfying 4 > r > 2.
  • alkoxysilicons examples include tetramethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, normal
  • butyltrimethoxysilane isobutyltrimethoxysilane, sec-butyltrimethoxysilane, tert-butyltrimethoxysilane, normal pentyltrimethoxysilane, tert- amyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, di-normal butyldimethoxysilane, diisobutyldimethoxysilane, di-tert- butyldimethoxysilane, methylethyldimethoxysilane, methyl-normal- propyldimethoxysilane, methyl-normal-butyldimethoxysilane,
  • cyclohexylisopropyldimethoxysilane cyclohexyl-normal- butyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyHert- butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane,
  • phenylmethyldimethoxysilane phenylethyldimethoxysilane, phenyl-normal - propyldimethoxysilane, phenylisopropyldimethoxysilane, phenyl-normal - butyldimethoxysilane, phenylisobutyldimethoxysilane, phenyHert- butyldimethoxysilane, phenylcyclopentyldimethoxysilane, 2- norbornanemethyldimethoxysilane, bis(perhydroquinolino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, (perhydroquinolino)
  • Examples thereof include compounds in which methoxy of these compounds is replaced by ethoxy, propoxy, normal butoxy, isobutoxy, tert-butoxy or phenoxy. Dialkyldialkoxysilane or trialkylmonoalkoxysilane is preferred, and trialkylmonoalkoxysilane is more preferred.
  • ethers examples include a dialkyl ether, an alkylaryl ether, a diaryl ether, a diether compound, cyclic ethers and cyclic diethers.
  • ether examples include dimethyl ether, diethyl ether, di- normal-propyl ether, diisopropyl ether, di-normal-butyl ether, diisobutyl ether, drtert-butyl ether, dicyclohexyl ether, diphenyl ether, methyl ethyl ether, methyl-normal-propyl ether, methyl isopropyl ether, methyl-normal- butyl ether, methyl isobutyl ether, methyl-tert-butyl ether, methyl
  • cyclohexyl ether methylphenyl ether, ethylene oxide, propylene oxide, oxetane, tetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1, 2 -diethoxy ethane, 1,2-diisobutoxyethane, 2,2- dimethoxypropane, 1,3-dimethoxypropane, 2,2-diisobutyl-l,3- dimethoxypropane, 2-isopropyl"2-isopentyl- 1,3-dimethoxypropane, 2,2- bis(cyclohexylmethyl)-l,3-dimethoxypropane, 2-isopropyl-2-3,7- dimethy locty 1 -1,3- dime thoxyp rop ane , 2 , 2 - diisopropyl- 1 , 3 - dimethoxyp
  • the ether is preferably diethyl ether, di-normal-butyl ether, methyl-normal- butyl ether, methylphenyl ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane or 1,3-dioxolane, and more preferably diethyl ether, di-normal-butyl ether or tetrahydrofuran.
  • carboxylic acid ester examples include mono or polyvalent carboxylic acid esters, and examples of the carboxylic acid ester include a saturated aliphatic carboxylic acid ester, an unsaturated aliphatic
  • carboxylic acid ester an alicyclic carboxylic acid ester and an aromatic carboxylic acid ester.
  • carboxylic acid ester examples include methyl acetate, ethyl acetate, normal butyl acetate, isobutyl acetate, tert-butyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, methyl benzoate, ethyl benzoate, normal butyl benzoate, isobutyl benzoate, tert-butyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, dimethyl succinate, diethyl succinate, di-normal-butyl succinate, dimethyl malonate, diethyl malonate, di-normal-butyl malonate
  • the carboxylic acid ester is preferably methyl acetate, ethyl acetate, methyl benzoate, ethyl benzoate, dimethyl phthalate, diethyl phthalate, di-normal- butyl phthalate, diisobutyl phthalate, dimethyl terephthalate or diethyl terephthalate, and still more preferably methyl benzoate, dimethyl phthalate, diethyl phthalate, diisobutyl phthalate or dimethyl terephthalate [0200]
  • amines include trihydrocarbylamine, and examples thereof include trimethylamine, triethylamine, tripropylamine, trinormal butylamine, triisobutylamine, trihexylamine, trioctylamine, tridodecylamine and triphenylamine. Triethylamine or trioctylamine is preferred.
  • the alkoxysilicons, the ethers or the amines are preferably used as the electron-donating compound (E).
  • the amines are more preferably used.
  • These electron-donating compounds (E) may be used alone, or two or more kinds of them may be used in combination.
  • the method for producing an addition polymer of the present invention includes the following two methods.
  • the first method is a method for producing an addition polymer, which includes the following steps ⁇
  • the second method is a method for producing an addition polymer, which includes the following steps:
  • solvent for polymerization examples include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane; aromatic hydrocarbon solvents such as benzene and toluene; and
  • halogenated hydrocarbon solvents such as dichloromethane.
  • the monomer per se can also be used as a solvent for polymerization, and examples of the monomer include ethylene, propylene, 1-butene, and 1-hexene.
  • the present invention includes the step of preparing a mixture by mixing a solvent for polymerization with the organic compound (D) represented by Formula [2].
  • the amount of the organic compound (D) based on the solvent for polymerization is usually within a range from 0.1 to 1,000 mg/L, more preferably from 1 to 100 mg/L, and still more preferably from 1.5 to 40 mg/L.
  • the solvent for polymerization and the organic compound (D) may be mixed in a polymerization reactor or, after mixing the solvent for polymerization with the organic compound (D) in advance, the mixture may be charged into a polymerization reactor.
  • the organic compound (D) may be mixed with the solvent after introducing the monomer into the solvent for polymerization.
  • a preferable method is a method in which a mixture is prepared by mixing the solvent for polymerization and the organic compound (D), a catalyst is prepared by mixing the compound (A), the activating agent (B) and if necessary, the organic compound (C) with the mixture, and then a monomer is introduced into the mixture and polymerization is performed by the catalyst.
  • the method of mixing the solvent for polymerization with the organic compound (D) includes a method in which the solvent for polymerization and the organic compound (D) are mixed as they are; a method in which the organic compound (D) is once mixed with the same solvent as the solvent for polymerization, and then the mixture is mixed with the solvent for polymerization; a method in which the organic compound (D) is once mixed with a solvent different from the solvent for polymerization, and then the mixture is mixed with the solvent for polymerization; a method in which the organic compound (D) is added to the solvent for polymerization, together with an inert gas flow; and a method in which the organic compound (D) is added to the solvent for polymerization, together with a monomer gas flow.
  • the solvent for polymerization preferably has been stirred.
  • the temperature at which the solvent for polymerization is mixed with the organic compound (D) is usually from 0°C to 150°C, preferably from 5°C to 100°C, and more preferably from 10°C to 80°C.
  • the mixture prepared by mixing the solvent for polymerization with the organic compound (D) can be used for polymerization immediately after its preparation, or a mixture is prepared by mixing the solvent for polymerization with the organic compound (D) and then the mixture can be used for polymerization after a while. In the latter case, the mixture is preferably used for polymerization within 5 hours, more preferably 3 hours, and still more preferably 1 hour after preparation of the mixture. [0211]
  • the catalyst in the present invention is obtained by bringing the compound (A), the activating agent (B) and if necessary, the
  • the amount of the compound (A) based on the amount of the activating agent (B) is usually from 0.1 to 1,000 ⁇ /g, preferably from 1 to 500 ⁇ /g, and more preferably from 10 to 300 ⁇ /g.
  • the amount of the organoaluminum compound (C) based on the amount of the compound (A) is usually from 0.01 to 10,000 mmol/g, preferably from 0.1 to 1,000 mmol/g, and more preferably from 0.5 to 200 mmol/g.
  • ⁇ 13> a method in which a contact product produced by bringing the above respective components into contact with one another is supplied in a polymerization reactor;
  • ⁇ 14> a method in which the above respective components are separately supplied in a polymerization reactor and these components are brought into contact with one another in the polymerization reactor;
  • ⁇ 15> a method in which any components of the above respective components are brought into contact with one another to obtain a precontact product before supplying the components in a polymerization reactor, and the precontact product is brought into contact with the remaining component(s) in the polymerization reactor.
  • the contact method is preferably ⁇ 14> described above.
  • the compound (A) may be supplied into a polymerization reactor in a powder or a slurry state of being suspended in a solvent.
  • a preferred method is that the respective components, a contact product obtained by bringin the respective components into contact with one another, or a precontact product is supplied into a polymerization reactor in which a mixture obtained by mixing the solvent for
  • ⁇ 16> an order in which a contact product produced by bringing the compound (A) into contact with the activating agent (B) is brought into contact with the organoaluminum compound (C);
  • ⁇ 17> an order in which a contact product produced by bringing the compound (A) into contact with the organoaluminum compound (C) is brought into contact with the activating agent (B);
  • ⁇ 21> an order in which a contact product produced by bringing the compound (A) into contact with the organoaluminum compound (C) is brought into contact with a contact product produced by bringing the compound (A) into contact with the activating agent (B).
  • the contact order is preferably ⁇ 16> or ⁇ 17> described above.
  • a solvent may be used. It is preferred to use a solvent since an active spot can be efficiently formed.
  • the solvent to be used at the time of contact may be a solvent which does not deactivate an active spot to be produced.
  • the solvent is more preferably a solvent which dissolves the compound (A).
  • the solvent include aliphatic hydrocarbon solvents such as butane, pentane, hexane, and octane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; halogenated hydrocarbon solvents such as dichloromethane; and polar solvents such as ethers, esters, and ketones.
  • a preferred solvent is a solvent which does not dissolve the produced addition polymer.
  • aliphatic hydrocarbon solvents are preferable.
  • the monomer may be present at the time of contact.
  • the temperature can be optionally set.
  • the temperature is usually from -50°C to 100°C, preferably from -30°C to 80°C, and more preferably from -10°C to 60°C.
  • the contact time can be optionally set. It is usually from substantially 0 minute to 24 hours, preferably from 1 minute to 12 hours, and more preferably from 3 minutes to 10 hours. When the components are charged continuously, the contact time is 0.
  • An addition polymerization method using a catalyst is a method of addition polymerizing monomers using a catalyst in a solvent.
  • Examples of the addition polymerization method using a catalyst include a solution polymerization method in which monomers are polymerized in a solvent, a slurry polymerization method (a suspension polymerization method), and a bulk polymerization method in which monomers as a solvent are
  • the addition polymerization using a catalyst can be carried out in a batch manner or a continuous manner.
  • the polymerization time of the addition polymerization using a catalyst is commonly determined according to the kind of the objective addition polymer and the polymerization reactor to be used, and is usually from 1 minute to 20 hours.
  • the addition polymerization using a catalyst can be carried out according to publicly-known methods and conditions.
  • a preferred method thereof is a method in which monomers, a solvent and, optionally, other materials to be supplied are continuously or intermittently supplied to a polymerization reactor, and then the produced addition polymer is continuously or intermittently extracted from the polymerization reactor. It is possible to use, as the polymerization reactor, a loop reactor, a reactor equipped with a stirrer, and a reactor in which a plurality of reactors equipped with a stirrer, each having a different type and a different polymerization reaction condition, are connected in series, in parallel or a combination thereof.
  • the solvent for polymerization, the polymerization temperature and the polymerization pressure are selected so that the solvent and at least a portion of the monomer can be maintained in a liquid phase and the monomer can be brought into contact with the catalyst.
  • polymerization temperature is usually from about -50°C to about 150°C.
  • the polymerization pressure is usually from about 0.001 MPa to about 10 MPa.
  • a catalyst or a component to be used so as to obtain the catalyst, and a monomer can be supplied to the polymerization reactor in any order by publicly -known methods.
  • Examples of a method of supplyng them to the polymerization reactor include (l) a method in which a catalyst or components to be used so as to obtain the catalyst, and monomers are simultaneously supplied to the polymerization reactor containing a mixture obtained by mixing a solvent for polymerization with the organic compound (D), and (2) a method in which a catalyst or components to be used so as to obtain the catalyst, and monomers are successively supplied to the polymerization reactor
  • a method of prepolymerizing monomers capable of addition polymerization using a catalyst to obtain a prepolymerized catalyst component for addition polymerization is particularly referred to as a prepolymerization method.
  • the prepolymerized catalyst component for addition polymerization may be sometimes referred to as a prepolymerized catalyst component.
  • the prepolymerization can be carried out in the same method and conditions as in the above-mentioned addition polymerization.
  • the prepolymerization can be carried out in a batch manner or a continuous manner.
  • the prepolymerization can be carried out in two or more stages, each having a different reaction condition.
  • the prepolymerization time is appropriately determined according to the kind of the objective olefin polymer and a reactor, and can be within a range from 1 minute to 20 hours.
  • the prepolymerization temperature is preferably from ⁇ 50°C to 100°C, more preferably from -30°C to 80°C, and still more preferably from -10°C to 60°C. The temperature may be changed during the prepolymerization.
  • the pressure at the time of the prepolymerization is usually from 0.001 MPa to 5 MPa, and preferably from 0.01 MPa to 2 MPa.
  • a catalyst, components to be used so as to obtain the catalyst, and monomers can be supplied to the polymerization reactor by the same method as in the above- mentioned addition polymerization.
  • the method is preferably a method of supplying the powdery compound (A) to the polymerization reactor.
  • prepolymerized catalyst component may be used for main polymerization, together with the solvent for polymerization.
  • the prepolymerized catalyst component is separated from the solvent for polymerization and the prepolymerized catalyst component separated is subjected to a treatment such as demonomerization, solvent distillation, filtration, washing, and drying to obtain a prepolymerized catalyst component in a solid state, and the resultant prepolymerized catalyst component may be used for the main polymerization.
  • the content of fine powders in the prepolymerized catalyst component is evaluated, for example, by the content of particles having a diameter of 60 ⁇ or less.
  • the content of particles having a diameter of 60 ⁇ or less in the prepolymerized catalyst component is preferably from 7.0% or less, more preferably from 5.0% or less, still more preferably from 2.0% or less, and particularly preferably from 0.8% or less.
  • the content of fine powders in the prepolymerized catalyst component can be adjusted, for example, by the median diameter or SPAN of the activating agent (B) to be used in the prepolymerization, and the kind of the organic compound (D) to be mixed with the solvent for polymerization.
  • the prepolymerization is carried out so that the amount of the polymer produced by prepolymerization can be within a range from 0.1 to 1,000 g, preferably from 0.5 to 500 g, more preferably from 1 to 100 g per gram of the component (B).
  • the amount of the polymer produced by prepolymerization is sometimes referred to as the degree of
  • prepolymerized catalyst component is referred to as main polymerization.
  • the prepolymerized catalyst component obtained may be used as it is as a catalyst for addition polymerization, and a contact product of the prepolymerized catalyst component and the
  • organoaluminum compound may be used as a catalyst for addition
  • the organoaluminum compound for the latter case the organoaluminum compound exemplified as the compound (C) is used.
  • the amount thereof to be used is usually from 1 to 10,000 mol/mol, preferably from 10 to 5,000 mol/mol, and more preferably from 30 to 1,000 mol/mol, based on the compound (A).
  • organoaluminum compound (C) are used after bringing them into contact with each other, the prepolymerized catalyst component and the
  • organoaluminum compound (C) can be supplied into a polymerization reactor in any order, or they may be supplied into a polymerization reactor after bringing them into contact with each other in advance.
  • a method of supplying the prepolymerized catalyst component and organoaluminum compound (C) to a reactor for catalyst preparation, or a polymerization reactor for the main polymerization examples include a method in which the prepolymerized catalyst component and the organoaluminum compound (C) are supplied in a solid state, ' a method in which the prepolymerized catalyst component and the organoaluminum compound (C) are supplied in the state of being dissolved, suppended or slurried in a hydrocarbyl solvent from which components causing deactiviation of a catalyst component such as moisture and oxygen have been sufficiently removed.
  • hydrocarbyl solvent examples include aliphatic hydrocarbyl solvents such as butane, pentane, hexane, heptane, and octane! aromatic hydrocarbyl solvents such as benzene and toluene! and halogenated hydrocarbyl solvents such as dichloromethane, and among them, aliphatic hydrocarbyl solvents or aromatic hydrocarbyl solvents are preferable, and aliphatic hydrocarbyl solvents are more preferable.
  • aliphatic hydrocarbyl solvents such as butane, pentane, hexane, heptane, and octane! aromatic hydrocarbyl solvents such as benzene and toluene! and halogenated hydrocarbyl solvents such as dichloromethane, and among them, aliphatic hydrocarbyl solvents or aromatic hydrocarbyl solvents are preferable, and aliphatic hydrocarbyl solvents are more preferable.
  • a polymerization method in the main polymerization there is no particular limitation on a polymerization method in the main polymerization.
  • the method include (l) a gas phase polymerization method of polymerizing gaseous monomers, (2) a solution polymerization method of polymerizing monomers in a solvent, or a slurry polymerization method (suspension polymerization method), and (3) a bulk polymerization method of polymerizing liquid monomers in the solvent consisting of the liquid monomers.
  • the main polymerization can be carried out in a batch manner or a continuous manner. Furthermore, the main prepolymerization can be carried out in two or more stages, each having a different reaction condition.
  • the polymerization time of the main polymerization is appropriately determined according to the kind of the objective addition polymer and the polymerization reactor to be used, arid is usually within a range from 1 minute to 20 hours.
  • the polymerization can be carried out according to the publicly-known methods and conditions.
  • a preferred method thereof is a method in which monomers, a diluent and, optionally, other materials to be supplied are continuously or intermittently supplied to a polymerization reactor, and then the produced addition polymer is continuously or intermittently extracted from the polymerization reactor.
  • the polymerization reactor include a loop reactor, a reactor equipped with a stirrer, and a reactor in which a plurality of reactors equipped with a stirrer, each having a different type and a different polymerization reaction condition, are connected in series, in parallel or a combination thereof.
  • the reactor for the gas phase polymerization is a fluidized bed type reaction vessel, and preferably a fluidized bed type reaction vessel with an enlarged portion.
  • the reactor may have a stirring blade in the reaction vessel.
  • Examples of a method in which the prepolymerized catalyst component is supplied to a reactor include a method in which the catalyst component is supplied in a state free from moisture usually together with an inert gas such as nitrogen or argon, hydrogen or ethylene; or a method in which the catalyst component is supplied in a state of a solution prepared by dissolving the prepolymerized catalyst component in a solvent or in a state of a slurry prepared by diluting the prepolymerized catalyst component with the solvent.
  • an inert gas such as nitrogen or argon, hydrogen or ethylene
  • the main polymerization is gas phase polymerization
  • the polymerization temperature of the gas phase polymerization there is no particular limitation on the polymerization temperature of the gas phase polymerization, as long as the polymerization temperature is lower than the melting temperature of a addition polymer to be produced, and it is preferably from 0°C to 150°C, and particularly preferably from 30°C to 100°C.
  • hydrogen may be added as a molecular weight modifier.
  • the polymerization may be carried out in an inert gas.
  • the method for producing an addition polymer of the present invention is a method for producing an addition polymer comprising addition polymerizing monomers capable of addition polymerization in the presence of the above catalyst or the prepolymerized catalyst for addition polymerization.
  • Examples of the monomer in the method for producing an addition polymer of the present invention include an olefin, a diolefin, a cyclic olefin, an alkenylaromatic hydrocarbyl and a polar monomer, each having 2 to 20 carbon atoms. Two or more kinds of monomers can be used.
  • Examples of the monomer include olefins such as ethylene,
  • propylene 1-butene, 1-pentene, 4-methyl-l-pentene, 5-methyl-l-hexene, 1- hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and vinylcyclohexane;
  • diolefins such as 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl- 1,4-hexadiene, 5-methyl- 1,4- hexadiene, 7-methyl-l,6-octadiene, 5-ethylidene-2-norbornene,
  • dicyclopentadiene 5-vinyl-2-norbornene, norbornadiene, 5-methylene-2- norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene and 1,3-cyclohexadiene; cyclic olefins such as norbornene, 5-methyl-2- norbornene, 5-ethyl"2-norbornene, 5"butyl-2-norbornene, 5-phenyl-2- norbornene, 5-benzyl"2-norbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8- methyltet
  • the monomer is preferably an olefin having 2 to 20 carbon atoms.
  • the olefin include ethylene, propylene, 1-butene, 1-pentene, 1- hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl- 1-pentene, 4- methyl-2-pentene, vinylcyclohexane and the like.
  • the monomer to be used in the prepolymerization is particularly preferably ethylene.
  • ethylene and cr olefin are preferably used.
  • the combination of monomers to be used is preferably a combination of ethylene and propylene, a combination of ethylene and 1-butene, a combination of ethylene and 1-hexene, a
  • the addition polymer obtained by the production method of the present invention is particularly preferably a copolymer of ethylene and cr olefin, and among them, a copolymer of ethylene and a-olefin having a polyethylene crystal structure is preferable.
  • the a-olefin is preferably an a-olefin having 3 to 8 carbon atoms, and examples thereof include 1-butene, 1-hexene, and 1-octene.
  • F A sample was combusted in a flask filled with oxygen and the generated combustion gas was absorbed in an aqueous sodium hydroxide solution (10%), and then F in the obtained aqueous solution was quantitatively determined using an ionic electrode method.
  • MFR is a melt flow rate (unit: g/io minutes) measured at 190°C under a load of 21.18 N (2.16 kg) in accordance with the method defined in JIS K7210-1995.
  • Swell ratio SR: A value which is obtained by dividing a strand diameter obtained at the time of the measurement of MFR by an inner diameter (2.095 mm) of a die used for measureing MFR.
  • a prepolymerized catalyst component for addition polymerization was dispersed in a dry state and the particle size distribution thereof was measured under the following conditions using a laser diffraction particle size distribution measurement apparatus HELOS&RODOS system manufactured by SYMPATEC GmbH.
  • the amount of a prepolymerized catalyst component for addition polymerization having a particle diameter of 60 ⁇ or less was calculated expressed by volume.
  • 192 mg (360 ⁇ ) of ethylenebis(indenyl)zirconium diphenoxide (A) was added to the autoclave, followed by stirring at 50°C for 1 hour and further cooling to 30°C.
  • 1 g of ethylene was added and 7.0 g of the activating agent (B) obtained in the above (l) was added.
  • the monomer and butane were purged, and then a prepolymerized catalyst component for addition polymerization was recovered.
  • the recovered amount was 131.7 g, and the degree of polymerization per activating agent (B) was 18.7 g/g.
  • the particle size distribution of the prepolymerized catalyst component was measured, and as a result, the amount of particles having a particle diameter of 60 pm or less contained in the prepolymerized catalyst component was 1.9%.
  • ethylenebis(indenyl)zirconium diphenoxide (A) and 2.0 ml of a solution of sodium polyoxyethylene lauryl acetate (n 10) (KAOAKYPO RLM-100NV, manufactured by Kao Corporation) (D) in hexane, the concentration of which had been adjusted to 10 mg/ml, were added.
  • the recovered amount was 131.2 g and the degree of polymerization per activating agent (B) was 18.7 g/g.
  • the particle size distribution of the prepolymerized catalyst component was measured, and as a result, the amount of particles having a particle diameter of 60 pm or less contained in the prepolymerized catalyst component was 0.8%.
  • an argon- substituted autoclave (inner volume of 5 L) equipped with a stirrer was evacuated, and hydrogen was added at a partial pressure of 0.037 MPa, and then 154 g of hexene-1 and 1,046 g of butane were supplied into the autoclave and the temperature was raised to 70°C. Then, ethylene was added so that the partial pressure thereof might become 1.6 MPa, and the system was stabilized. As a result of gas
  • 381.3 mg of the prepolymerized catalyst component obtained in the above (l) was supplied.
  • an ethylene/hydrogen mixed gas hydrogen ⁇ 0.295 mol%
  • ethylenebis(indenyl) zirconium diphenoxide (A) and 5.0 ml of a solution of sodium polyoxyethylene lauryl acetate (n 10) (KAOAKYPO RLM-100NV, manufactured by Kao Corporation) (D) in hexane, the concentration of which had been adjusted to 10 mg/ml, were added.
  • the recovered amount was 129.2 g and the degree of polymerization per activating agent (B) was 18.2 g/g.
  • the particle size distribution of the prepolymerized catalyst component was measured, and as a result, the amount of particles having a particle diameter of 60 ⁇ or less contained in the prepolymerized catalyst component was 1.5%.
  • Example 1(2) except that 205mg (384 ⁇ ) of
  • ethylenebis(indenyl)zirconium diphenoxide (A) and 30.0 ml of a solution of sodium polyoxyethylene lauryl acetate (n 10) (KAOAKYPO RLM-100NV, manufactured by Kao Corporation) (D) in hexane, the concentration of which had been adjusted to 10 mg/ml, were added.
  • the recovered amount was 143.9 g and the degree of polymerization per activating agent (B) was 20.4 g/g.
  • the particle size distribution of the prepolymerized catalyst component was measured, and as a result, the amount of particles having a particle diameter of 60 ⁇ or less contained in the prepolymerized catalyst component was 0.4%.
  • an argon-substituted autoclave (inner volume of 5 L) equipped with a stirrer was evacuated, and hydrogen was added at a partial pressure of 0.037 MPa, and then 154 g of hexene-1 and 1,046 g of butane were supplied into the autoclave and the temperature was raised to 70°C. Then, ethylene was added so that the partial pressure thereof might become 1.6 MPa, and the system was stabilized. As a result of gas
  • 409.8 mg of the prepolymerized catalyst component obtained in the above (l) was supplied.
  • an ethylene hydrogen mixed gas hydrogen 0.300 mol%
  • ethylenebis(indenyl)zirconium diphenoxide (A) and 5.0 ml of a solution of sodium polyoxyethylene lauryl sulfate (n 2) (EMAL 270J, manufactured by Kao Corporation) (D) in hexane, the concentration of which had been adjusted to 10 mg/ml, were added.
  • the recovered amount was 123.0 g and the degree of polymerization per activating agent (B) was 17.5 g/g.
  • the particle size distribution of the prepolymerized catalyst component was measured, and as a result, the amount of particles having a particle diameter of 60 pm or less contained in the prepolymerized catalyst component was 5.3%.
  • an argon-substituted autoclave (inner volume of 5 L) equipped with a stirrer was evacuated, and hydrogen was added at a partial pressure of 0.037 MPa, and then 154 g of hexene-1 and 1,046 g of butane were supplied into the autoclave and the temperature was raised to 70°C. Then, ethylene was added so that the partial pressure thereof might become 1.6 MPa, and the system was stabilized. As a result of gas
  • an argon-substituted autoclave (inner volume of 5 L) equipped with a stirrer was evacuated, and hydrogen was added at a partial pressure of 0.037 MPa, and then 154 g of hexene-1 and 1,046 g of butane were supplied into the autoclave and the temperature was raised to 70°C. Then, ethylene was added so that the partial pressure thereof might become 1.6 MPa, and the system was stabilized. As a result of gas
  • Example l(l) ethylenebis(indenyl)zirconium diphenoxide (A) and 7.0 g of the activating agent (B) obtained in Example l(l) were added, and the organic compound (D) was not added.
  • the recovered amount was 130.3 g and the degree of polymerization per activating agent (B) was 18.6 g/g.
  • the particle size distribution of the prepolymerized catalyst component was measured, and as a result, the amount of particles having a particle diameter of 60 ⁇ or less contained in the prepolymerized catalyst component was 11.0%.
  • an argon-substituted autoclave (inner volume of 5 L) equipped with a stirrer was evacuated, and hydrogen was added at a partial pressure of 0.037 MPa, and then 154 g of hexene-1 and 1,046 g of butane were supplied into the autoclave and the temperature was raised to 70°C. Then, ethylene was added so that the partial pressure thereof might become 1.6 MPa, and the system was stabilized. As a result of gas
  • 378.3 mg of the prepolymerized catalyst component obtained in the above (l) was supplied.
  • an ethylene/hydrogen mixed gas hydroogen 0.301 mol%

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