WO2008105546A1 - Procédé de production de polymère oléfinique - Google Patents

Procédé de production de polymère oléfinique Download PDF

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Publication number
WO2008105546A1
WO2008105546A1 PCT/JP2008/053709 JP2008053709W WO2008105546A1 WO 2008105546 A1 WO2008105546 A1 WO 2008105546A1 JP 2008053709 W JP2008053709 W JP 2008053709W WO 2008105546 A1 WO2008105546 A1 WO 2008105546A1
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WIPO (PCT)
Prior art keywords
component
titanium dichloride
phenoxy
dimethylsilylene
tert
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PCT/JP2008/053709
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English (en)
Inventor
Yasutoyo Kawashima
Tomoaki Goto
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Sumitomo Chemical Company, Limited
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Priority claimed from JP2007333995A external-priority patent/JP2008239954A/ja
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Priority to US12/528,421 priority Critical patent/US8410231B2/en
Priority to DE112008000517T priority patent/DE112008000517T5/de
Publication of WO2008105546A1 publication Critical patent/WO2008105546A1/fr

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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
    • 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
    • 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
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • the present invention relates to a production process of olefin polymer.
  • olefin-base polymers e.g., ethylene homopolymers and ethylene/ ⁇ - olefin copolymers
  • processes for producing olefin-base polymers include those carried out in the presence of a metallocene-base catalyst. These processes give polymers of higher mechanical strength, blocking capability and so forth than the conventional ones carried out in the presence of a Ziegler-Natta catalyst.
  • One of the known olefin production processes carried out in the presence of a metallocene-base catalyst comprises a step in which ethylene is preliminarily polymerized in the presence of a preliminary polymerization catalyst produced by bringing a metallocene-base complex, carrier and organoaluminum compound into contact with each other to produce a preliminary polymerization catalyst component; and a subsequent step in which ethylene and an ⁇ -olefin are copolymerized in a vapor-phase polymerization reactor in the presence of an organoaluminum compound of the similar species to that used in the preliminary polymerization step and the preliminary polymerization catalyst component.
  • Patent Document 1 JP-A-2005-97481
  • the present invention provides a process for producing an olefin polymer, comprising: the step (I) of preliminarily polymerizing an olefin at 65°C or lower in the presence of a preliminary polymerization catalyst prepared by bringing the following components (A) , (B) and (C) into contact with each other, to produce a preliminary polymerization catalyst component (X) ; and the step (II) of polymerizing an olefin in the presence of a polymerization catalyst prepared by bringing the preliminary polymerization catalyst component (X) into contact with the following component (D) , to produce an olefin polymer,- component (A) : a metallocene-base complex, component (B) : a solid co-catalyst component in which a compound capable of ionizing the metallocene-base complex into an ionic complex is supported on fine particle support, component (C) : an organoaluminum compound represented by the general formula RSAl (wherein
  • the present invention can provide a process of high polymerization activity for production of an olefin polymer in the presence of a metallocene-base catalyst .
  • the step (I) of the present invention is the step of preliminary polymerizing an olefin at 65°C or lower in the presence of a preliminary polymerization catalyst prepared by bringing the following components (A) , (B) and (C) into contact with each other, to produce a preliminary polymerization catalyst component (X) ;
  • component (A) a metallocene-base complex
  • component (B) a solid co-catalyst component in which a compound capable of ionizing the metallocene-base complex into an ionic complex is supported on fine particle support
  • component (C) an organoaluminum compound represented by the general formula RSAI (wherein, R 1 is a linear hydrocarbon group of 1 to 8 carbon atoms, wherein the R 1 can be the same or different) .
  • RSAI organoaluminum compound represented by the general formula RSAI (wherein, R 1 is a linear hydrocarbon group of 1 to 8 carbon atoms, wherein the R 1 can be the same or different
  • the metallocene-base complex as the component (A) is a transition metal compound having a cyclopentadiene type anion structure, preferably a transition metal compound represented by the general formula (1) or its ⁇ -oxo type dimer:
  • a is a numeral satisfying 0 ⁇ a ⁇ 8
  • b is a numeral satisfying 0 ⁇ b ⁇ 8
  • M is a transition element of groups 3 to 11 in the periodic table or of lanthanoid series
  • - L is a group having a cyclopentadiene type anion structure, wherein plural L may be bound to each other either directly or via a residue containing carbon, silicon, nitrogen, oxygen, sulfur or phosphorus atom
  • X is a halogen atom, hydrocarbon group (except for a group having a cyclopentadiene type anion structure) or hydrocarbonoxy group) .
  • M in the general formula (1) is a transition element of groups 3 to 11 in the periodic table (IUPAC, 1989) or of lanthanoid series. More specifically, they include scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, iron, ruthenium, cobalt, rhodium, nickel, palladium, samarium and ytterbium.
  • M is preferably a transition metal element of group 4, more preferably titanium, zirconium or hafnium, still more preferably zirconium.
  • L is a group having a cyclopentadiene type anion structure, wherein plural L may be the same or different, and bound to each other either directly or via a cross-linking group containing carbon, silicon, nitrogen, oxygen, sulfur or phosphorus atom.
  • the groups of L having a cyclopentadiene type anion structure include ⁇ 5 - (substituted) cyclopentadienyl group, ⁇ 5 - (substituted) indenyl group and ⁇ 5 - (substituted) fluorenyl group.
  • ⁇ 5 -cyclopentadienyl More specifically, they include ⁇ 5 -cyclopentadienyl, ⁇ 5 - methylcyclopentadienyl, ⁇ 5 -ethylcyclopentadienyl, ⁇ s -n- butylcyclopentadienyl, ⁇ 5 -tert-butylcyclopentadienyl, ⁇ 5 -l, 2-dimethylcyclopentadienyl, ⁇ 5 -l, 3- dimethylcyclopentadienyl, ⁇ 5 -1-methyl-2- ethylcyclopentadienyl , ⁇ 5 -1-methyl-3 - ethylcyclopentadienyl , ⁇ 5 -1-tert-butyl-2 - methylcyclopentadienyl, ⁇ 5 -l-tert-butyl-3- methylcyclopentadienyl , ⁇ 5 -1-methyl
  • the groups having a cyclopentadiene type anion structure may be bound to each other either directly or via a cross-linking group containing carbon, silicon, nitrogen, oxygen, sulfur or phosphorus atom.
  • the cross-linking groups for the present invention include alkylenes, e.g., ethylene and propylene; substituted alkylene groups, e.g., dimethylmethylene and diphenylmethylene ; silylene and substituted silylene and its substitutions, e.g., dimethylsilylene, diphenylsilylene and tetramethylsilylene,- and hetero atoms, e.g., nitrogen, oxygen, sulfur and phosphorus.
  • X is a halogen atom, hydrocarbon group (except for a group having a cyclopentadiene type anion structure) or hydrocarbonoxy group. More specifically, the halogen atoms include fluorine, chlorine, bromine and iodine.
  • the hydrocarbon group does not include a group having a cyclopentadiene type anion structure.
  • the hydrocarbon groups include alkyl, aralkyl, aryl and alkenyl etc.
  • the hydrocarbonoxy groups include alkoxy, aralkyloxy and aryloxy etc.
  • the alkyl groups include methyl, ethyl, n- propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, neopentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl and n-eicosyl, each of which may be substituted by a halogen atom, e.g., fluorine, chlorine, bromine or iodine.
  • a halogen atom e.g., fluorine, chlorine, bromine or iodine.
  • the alkyl groups substituted by a halogen atom include fluoromethyl, trifluoromethyl, chloromethyl, trichloromethyl, fluoroethyl, pentafluoroethyl, perfluoropropyl, perfluorobutyl, perfluorohexyl, perfluorooctyl, perchloropropyl , perchlorobutyl and perbromopropyl .
  • Each of these alkyl groups may be partly substituted by an alkoxy group, e.g., methoxy or ethoxy; aryloxy group, e.g., phenoxy; or aralkyloxy group, e.g., benzyloxy.
  • the aralkyl groups include benzyl, (2- methylphenyl) methyl, (3 -methylphenyl) methyl, (4- methylphenyl) methyl, (2, 3-dimethylphenyl) methyl, (2,4- dimethylphenyl) methyl, (2, 5-dimethylphenyl) methyl, (2, 6-dimethylphenyl) methyl, (3 , 4 -dimethylphenyl) methyl, (3, 5-dimethylphenyl) methyl, (2,3,4- trimethylphenyl) methyl, (2,3, 5-trimethylphenyl) methyl, (2,3, 6-trimethylphenyl) methyl, (3,4,5- trimethylphenyl) methyl , (2,4, 6-trimethylphenyl) methyl , (2,3,4,5-tetramethylphenyl) methyl , (2,3,4,6- tetramethylphenyl) methyl, (2,3,5,6- tetramethylphenyl) methyl , (pentamethyl
  • Each of these aralkyl groups may be partly substituted by a halogen atom, e.g., fluorine, chlorine, bromine or iodine; alkoxy group, e.g., methoxy or ethoxy,- aryloxy group, e.g., phenoxy; or aralkyloxy group, e.g., benzyloxy.
  • a halogen atom e.g., fluorine, chlorine, bromine or iodine
  • alkoxy group e.g., methoxy or ethoxy,- aryloxy group, e.g., phenoxy
  • aralkyloxy group e.g., benzyloxy.
  • the aryl groups include phenyl, 2-tolyl, 3- tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6- xylyl, 3,4-xylyl, 3,5-xylyl, 2, 3, 4 -trimethylphenyl, 2,3, 5-trimethylphenyl, 2, 3, 6-trimethylphenyl, 2,4,6- trimethylphenyl, 3, 4, 5-trimethylphenyl, 2,3,4,5- tetramethylphenyl , 2, 3,4, 6-tetramethylphenyl, 2,3,5,6- tetramethylphenyl, pentamethylphenyl , ethylphenyl, n- propylphenyl, isopropylphenyl , n-butylphenyl , sec- butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylpheny
  • Each of these aryl groups may be partly substituted by a halogen atom, e.g., fluorine, chlorine, bromine or iodine,- alkoxy group, e.g., methoxy or ethoxy; aryloxy group, e.g., phenoxy,- or aralkyloxy group, e.g., benzyloxy.
  • a halogen atom e.g., fluorine, chlorine, bromine or iodine
  • - alkoxy group e.g., methoxy or ethoxy
  • aryloxy group e.g., phenoxy,- or aralkyloxy group, e.g., benzyloxy.
  • the alkenyl groups include allyl, methallyl, crotyl and 1, 3-diphenyl-2-propenyl groups.
  • the alkoxy groups include methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, neopentoxy, n-hexoxy, n-octoxy, n-dodesoxy, n-pentadesoxy and-n-icosoxy groups.
  • Each of these alkoxy groups may be partly substituted by a halogen atom, e.g., fluorine, chlorine, bromine or iodine; alkoxy group, e.g., methoxy or ethoxy; aryloxy group, e.g., phenoxy; or aralkyloxy group, e.g., benzyloxy.
  • a halogen atom e.g., fluorine, chlorine, bromine or iodine
  • alkoxy group e.g., methoxy or ethoxy
  • aryloxy group e.g., phenoxy
  • aralkyloxy group e.g., benzyloxy.
  • the alkoxy groups include methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, neopentoxy, n-hexoxy, n-octoxy, n-dodesoxy, n-pentadesoxy and-n-icosoxy groups.
  • Each of these alkoxy groups may be partly substituted by a halogen atom, e.g., fluorine, chlorine, bromine or iodine,- alkoxy group, e.g., methoxy or ethoxy; aryloxy group, e.g., phenoxy; or aralkyloxy group, e.g., benzyloxy.
  • a halogen atom e.g., fluorine, chlorine, bromine or iodine
  • - alkoxy group e.g., methoxy or ethoxy
  • aryloxy group e.g., phenoxy
  • aralkyloxy group e.g., benzyloxy.
  • the aralkyloxy groups include benzyloxy, (2- methylphenyl) methoxy, (3 -methylphenyl) methoxy, (4- methylphenyl) methoxy, (2 , 3 -dimethylphenyl) methoxy, (2, 4 -dimethylphenyl) methoxy, (2,5- dimethylphenyl) methoxy, (2 , 6-dimethylphenyl) methoxy, (3, 4-dimethylphenyl)methoxy, (3,5- dimethylphenyl) methoxy, (2,3, 4 -trimethylphenyl) methoxy, (2,3,5-trimethylphenyl) methoxy, (2,3,6- trimethylphenyl) methoxy, (2,4,5- trimethylphenyl) methoxy, (2,4,6- trimethylphenyl) methoxy, (3,4,5- trimethylphenyl) methoxy, (2,3,4,5- tetramethylphenyl) methoxy, (2,3,4,6-
  • alkoxy group e.g., methoxy or ethoxy,- aryloxy group, e.g., phenoxy; or aralkyloxy group, e.g., benzyloxy.
  • the aryloxy groups include phenoxy, 2- methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3- dimethylphenoxy, 2 , 4 -dimethylphenoxy, 2,5- dimethylphenoxy, 2, 6-dimethylphenoxy, 3,4- dimethylphenoxy, 3 , 5-dimethylphenoxy, 2-tert-butyl-3 - methylphenoxy, 2 -tert-butyl-4-methylphenoxy, 2-tert- butyl-5-methylphenoxy, 2 -tert-butyl-6-methylphenoxy, 2 , 3 , 4-trimethylphenoxy, 2, 3, 5-trimethylphenoxy, 2,3,6- trimethylphenoxy, 2,4, 5-trimethylphenoxy, 2,4,6- trimethylphenoxy, 2-tert-butyl-3 , 4-dimethylphenoxy, 2- tert-butyl-3, 5-dimethylphenoxy, 2 -tert-butyl-3 , 6- dimethylphenoxy, 2, 6-di-tert-butyl-3-methylphenoxy,
  • Each of these aryloxy groups may be partly substituted by a halogen atom, e.g., fluorine, chlorine, bromine or iodine,- alkoxy group, e.g., methoxy or ethoxy; aryloxy group, e.g., phenoxy,- or aralkyloxy group, e.g., benzyloxy.
  • a halogen atom e.g., fluorine, chlorine, bromine or iodine
  • - alkoxy group e.g., methoxy or ethoxy
  • aryloxy group e.g., phenoxy,- or aralkyloxy group, e.g., benzyloxy.
  • a is a numeral satisfying 0 ⁇ a ⁇ 8; ⁇ b" is a numeral satisfying 0 ⁇ b ⁇ 8, adequately selected depending on valence of M, wherein X ⁇ a" is preferably 2 and “b” is also preferably 2 when M is a transition metal element of group 4 in the periodic table (IUPAC, 1989) .
  • Metallocene-base complexes with two cyclopentadiene type anion structures include bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (ethylcyclopentadienyl) titanium dichloride, bis(n- butylcyclopentadienyl) titanium dichloride, bis(tert- butylcyclopentadienyl) titanium dichloride, bis (1,2- dimethylcyclopentadienyl) titanium dichloride, bis (1,3- dimethylcyclopentadienyl) titanium dichloride, bis(l- methyl-2-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-3 -ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-3 -n-butylcyclopentadien
  • Metallocene-base complexes with two cyclopentadiene type anion structures bound to each other via a cross-linking group include dimethylsilylenebis (cyclopentadienyl) titanium dichloride, dimethylsilylenebis (2- methylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3 -methylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2-n- butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3- dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2, 4-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2, 5- dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3 , 4-dimethylcyclopentadien
  • Metallocene-base complexes with one cyclopentadiene type anion structure include cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, cyclopentadienyl (dimethylamide) titanium dichloride, cyclopentadienyl (phenoxy) titanium dichloride, cyclopentadienyl (2, 6-dimethylphenyl) titanium dichloride, cyclopentadienyl (2, 6-diisopropylphenyl) titanium dichloride, cyclopentadienyl (2, 6-di-tert- butylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2, 6-di-methylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6- diisopropylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,
  • 2-phenoxy) titanium dichloride dimethylsilylene (tert- butyleyelopentadienyl) (3, 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert- butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert- butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert- butylcyclopentadienyl) (3, 5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert- butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert- butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5- methyl-2-phenoxy) titanium dich
  • dimethylsilylene (fluorenyl) (2-phenoxy) titanium dichloride dimethylsilylene (fluorenyl) (3-methyl-2- phenoxy) titanium dichloride, dimethylsiIyIene (fluorenyl) (3 , 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsiIyIene (fluorenyl) (3- tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methyl-2- phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3, 5-di-tert-butyl-2- phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3 -phenyl-2- phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyldimethylsilyl-
  • 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, [0037] (tert-butylamide) tetramethylcyclopentadienyl-1, 2- ethanediyl titanium dichloride,
  • ⁇ -oxo type transition metal compounds represented by the general formula (1) include ⁇ - oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride] , ⁇ - oxobis [isopropylidene (cyclopentadienyl) (3-tert-butyl-5- methyl-2-phenoxy) titanium chloride] , ⁇ - oxobis [isopropylidene (methylcyclopentadienyl) (2- phenoxy) titanium chloride] , ⁇ - oxobis [isopropylidene (methylcyclopentadienyl) (3-tert- butyl-5-methyl-2-phenoxy) titanium chloride] , ⁇ - oxobis [isopropylidene (tetramethylcyclopentadienyl) (2- phenoxy) titanium chloride] , ⁇ - oxobis tisopropylidene (tetra
  • the metallocene complex as the component (A) preferably has two cyclopentadiene type anion structures bound to each other via a cross-linking group, e.g., alkylene or silylene.
  • the metallic atoms for the metallocene complexes having two cyclopentadiene type anion structures bound to each other via a cross-linking group are preferably the group 4 metals in the periodic table, more preferably zirconium and hafnium.
  • the cyclopentadienyl type anion structure is preferably indenyl, methylindenyl, methylcyclopentadienyl or dimethylcyclopentadienyl group.
  • the cross-linking group is preferably ethylene, dimethylmethylene or dimethylsilylene.
  • the other substituent which the metal atom has is preferably diphenoxy or dialkoxy. Ethylenebis (1-indenyl) zirconium phenoxide can be cited as the more preferable metallocene-base complex.
  • the metallocene complex as the component (A) can be a combination of two or more kinds of complex.
  • At least one compound selected from the group consisting of boron compounds, zinc compounds and organoaluminum oxy compounds can be cited.
  • organoaluminum oxy compounds methyl aluminoxane and methylisobutyl aluminoxane can be sited. These compounds may be produced by a method of drying a commercial organoaluminum oxy compound under a vacuum such as a method disclosed by JP-A-2003-128718, or a method of washing the solid produced under a vacuum with a hydrocarbon solvent .
  • the compound for ionizing the metallocene complex into the ionic complex is preferably a boron or zinc compound.
  • the fine particle support (fine particulate carrier) for the component (B) is preferably a porous one.
  • These carriers include those of inorganic oxide, e.g., SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, BaO and ThO 2 ; clays and clay minerals, e.g., smectite, montmorillonite, hectorite, raponite and saponite,- and organic polymers, e.g., polyethylene, polypropylene and styrene-divinyl benzene copolymer.
  • the fine particulate carrier has a 50% volume-average particle diameter of normally 10 to 500 ⁇ m, which can be determined by light scattering laser diffractometry or the like. It has a pore volume of normally 0.3 to 10 mL/g, and specific surface area of normally 10 to 1000 m 2 /g. The pore volume and specific surface area are determined by gas adsorption method; the former by the BJH method for determining quantity of gas desorbed and the latter by the BET method for determining quantity of gas adsorbed. [0048]
  • the fine particulate carrier is preferably dried, preferably under heating, to be substantially free of moisture.
  • the drying temperature is preperably normally 100 to 1500 0 C for the carrier with moisture not confirmed visually, preferably 100 to 1000°C, more preferably 200 to 800°C.
  • the drying time is not limited, but preferably 10 minutes to 50 hours, more preferably 1 to 30 hours.
  • Some of the methods for drying the carrier under heating include heating in an inert gas (e.g., nitrogen or argon) flowing at a constant rate, or heating under a vacuum.
  • the solid co-catalyst component for the component (B) is a compound supported by the fine particulate carrier for ionizing the metallocene complex into the ionized complex.
  • the method for supporting the co-catalyst component is not limited so long as it brings the compound for ionizing the metallocene complex into contact with the carrier, in which the above compound may be produced in the presence of the carrier.
  • the treatment of bringing the compound into contact with the carrier is preferably carried out in an inert gas atmosphere.
  • the treatment temperature is normally -100 to 300°C, preferably -80 to 200°C.
  • the treatment time is normally 1 minute to 200 hours, preferably 10 minutes to 100 hours.
  • the treatment may be carried out in the presence of a solvent, or by direct contact of the compound and carrier in the absence of a solvent .
  • the solvent for the contacting treatment is inert to the compound for ionizing the metallocene complex into the ionized complex, normally selected from hydrocarbon solvents, such as aliphatic compounds, e.g., butane, pentane, hexane, heptane, octane, 2,2,4- trimethylpentane and cyclohexane,- and aromatic compounds, e.g., benzene, toluene and xylene.
  • hydrocarbon solvents such as aliphatic compounds, e.g., butane, pentane, hexane, heptane, octane, 2,2,4- trimethylpentane and cyclohexane,- and aromatic compounds, e.g., benzene, toluene and xylene.
  • component (B) examples include a support (carrier) produced by bringing diethyl zinc (component (a) ) , fluorinated phenol (component (b) ) , water (component (c) ) , fine inorganic particulate carrier (component (d) ) and alkyl disilazane (component (e) ) into contact with each other.
  • a support produced by bringing diethyl zinc (component (a) ) , fluorinated phenol (component (b) ) , water (component (c) ) , fine inorganic particulate carrier (component (d) ) and alkyl disilazane (component (e) ) into contact with each other.
  • the preferable compounds for the component (b) include 3 ,4, 5-trifluorophenol, 3,4,5- tris (trifluoromethyl) phenol, 3,4,5- tris (pentafluorophenyl) phenol, 3 , 5-difluoro-4- pentafluorophenylphenol and 4, 5, 6, 7, 8-pentafluoro-2- naphthol .
  • the fine inorganic particulate carrier as the component (d) is preferably silica gel .
  • composition of the (a) diethyl zinc, (b) fluorinated phenol and (c) water preferably satisfies the following relations:
  • the molar ratios "y” and “z” are not limited, so long as they satisfy the formulae (2) , (3) and (4) .
  • the polymerization activity may be insufficient.
  • the polymerization activity may be also insufficient.
  • "y” is normally 0.55 to 0.99, preferably 0.55 to 0.95, more preferably 0.6 to 0.9, most preferably 0.7 to 0.8.
  • (d) /diethyl zinc (a) molar ratio is preferably 0.1 mmol/mol or more, wherein the denominator is number of mols of atomic zinc derived from diethyl zinc and present in 1 g of the particulate carrier produced by bringing the component (a) into contact with the component (d) , more preferably 0.5 to 20 mmols/mol.
  • the trimethyl disilazane (e)/fine inorganic particulate carrier (d) molar ratio is preferably 0.1 mmol/mol or more, wherein the denominator is number of mols of trimethyl disilazane present in 1 g of the particulate carrier, more preferably 0.5 to 20 mmols/mol.
  • the order of contacting the component (a) , component (b) , component (c) , component (d) and component (e) is not limited. Normally, however, the components (a) and (b) are brought into contact with each other, components (d) and (e) are brought into contact with each other, and then the product of the contacted components (a) and (b) is brought into contact with that of the contacted components (d) and (e) , and finally with the component (c) .
  • the components (d) and (e) are brought into contact with each other, the product of the contacted components (d) and (e) is brought into contact with the component (a) , and the resultant product is brought into contact with the component (b) and finally with the component (c) .
  • the contacting treatment is carried out preferably in an inert gas atmosphere.
  • the treatment temperature is normally -100 to 300 0 C, preferably -80 to 200°C.
  • the treatment time is normally 1 minute to 200 hours, preferably 10 minutes to 100 hours.
  • the treatment may be carried out in the presence of a solvent, or by direct contact of these components in the absence of a solvent .
  • the solvent for the contacting treatment is inert to all of the components (a) to (e) . However, when the components are contacted stepwise, as described above, a solvent which is active to a component in a step may be used in another step so long as it is inert to the component in the another step.
  • the solvent is normally selected from hydrocarbon solvents, such as aliphatic compounds, e.g., butane, pentane, hexane, heptane, octane, 2,2,4- trimethylpentane and cyclohexane; and aromatic compounds, e.g., benzene, toluene and xylene.
  • hydrocarbon solvents such as aliphatic compounds, e.g., butane, pentane, hexane, heptane, octane, 2,2,4- trimethylpentane and cyclohexane
  • aromatic compounds e.g., benzene, toluene and xylene.
  • the component (C) of organoaluminum compound is represented by the general formula R ⁇ Al (wherein, R 1 is a linear hydrocarbon group of 1 to 8 carbon atoms, wherein the R 1 may be the same or different) .
  • the linear hydrocarbon groups of 1 to 8 carbon atoms for R 1 include methyl, ethyl, n-propyl, n-butyl and n-octyl.
  • the organoaluminum compounds for the component (C) include trimethyl aluminum, triethyl aluminum, tri-n- butyl aluminum and tri-n-octyl aluminum, of which triethyl aluminum is more preferable viewed from enhancing the polymerization activity. [0063]
  • the preliminary polymerization catalyst may be produced by mixing and bringing the components (A) , (B) and (C) into contact with each other in an inert solvent, such as saturated aliphatic hydrocarbon compounds, e.g., propane, n-butane, isobutene, n- pentane, isopentane, n-hexane, cyclohexane and heptane.
  • an inert solvent such as saturated aliphatic hydrocarbon compounds, e.g., propane, n-butane, isobutene, n- pentane, isopentane, n-hexane, cyclohexane and heptane.
  • the contacting treatment temperature is normally -20 to 100°C.
  • Quantity of the metallocene-base complex as the component (A) is preferably 5 ⁇ lO "6 to 5 ⁇ lO '4 mols per gram of the solid promoter component for the
  • the preferable molar ratio of the organoaluminum compound as the component (C) to be contacted to the metallocene-base complex (component (A)) is 0.1 to 10 as (Al/M) , wherein Al is aluminum in the organoaluminum compound and M is a transition metal in the metallocene-base complex.
  • the polymerization activity may be insufficient when the ratio is excessively low. It is more preferably 0.5 or more, and 5 or less viewed from increasing molecular weight of the polymer product.
  • an organoaluminum compound other than the component (C) may be present.
  • the component (C) preferably accounts for 20% by mol or more based on the total organoaluminum compounds used in the preliminary polymerization step, viewed from enhancing the polymerization activity, more preferably 50% by mol or more.
  • Step (1) in which a saturated aliphatic hydrocarbon compound as a solvent containing a metallocene-base complex as the component (A) is heat-treated at 40°C or higher,
  • Step (2) in which the heat-treated product of the step (1) is brought into contact with and treated with a solid promoter component as the component (B)
  • Step (3) in which the contacting-treated product of the step (2) is brought into contact with an organoaluminum compound as the component (C) .
  • the step (1) treats a saturated aliphatic hydrocarbon compound as a solvent , containing a metallocene-base complex as the component (A) under heating at 40 0 C or higher.
  • the saturated aliphatic hydrocarbon compound solvent containing the metallocene-base complex may be prepared by incorporating the solvent with the complex.
  • the metallocene-base complex is normally used in the form of powder or slurry with the saturated aliphatic hydrocarbon compound.
  • the saturated aliphatic hydrocarbon compounds useful for preparing the solvent containing the metallocene-base complex include propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane and heptane. They may be used either individually or in combination.
  • the compound preferably has a boiling point of 100 0 C or lower at normal pressure, more preferably 90°C or lower.
  • propane, n-butane, isobutane, n-pentane, isopentane, n- hexane and cyclohexane are more preferable . [0070].
  • the heat-treatment of the saturated aliphatic hydrocarbon compound solvent containing the metallocene-base complex may be carried out by adjusting the solvent temperature at 40°C or higher, while it is kept stationary or stirred.
  • the temperature is preferably 45°C or higher viewed from enhancing moldability of the polymer, more preferably 50 0 C or higher. It is preferably 100 0 C or lower viewed from enhancing catalyst activity, more preferably 80 0 C or lower.
  • the heat-treatment time is normally 0.5 to 12 hours. It is preferably 1 hour or more viewed from enhancing moldability, more preferably 2 hours or more. It is preferably 6 hours or less viewed from stability of the catalyst performance, more preferably 4 hours or less.
  • the step (2) brings the heat-treated product of the step (1), i.e., the saturated aliphatic hydrocarbon compound solvent containing the metallocene-base complex, into contact with a solid co- catalyst (promoter) component.
  • This step may be carried out by any method which can bring the heat- treated product with the solid promoter component, normally by incorporating the solid promoter component into the heat-treated product, or by incorporating the heat-treated product and solid promoter component into the saturated aliphatic hydrocarbon compound.
  • the solid promoter component is normally used in the form of powder or slurry with the saturated aliphatic hydrocarbon compound solvent .
  • the contacting treatment temperature for the step (2) is preferably 70°C or lower, more preferably 60°C or lower. It is also preferably 10°C or higher, more preferably 20°C or higher.
  • the contacting treatment time is normally 0.1 to 2 hours.
  • the step (3) brings the contacting-treated product of the step (2), i.e., product of contacting the heat-treated product of the step (1) and solid promoter component, into contact with an organoaluminum compound as the component (C) .
  • This step may be carried out by any method which can bring the contacting-treated product of the step (2) into contact with the organoaluminum compound as the component (C) , normally by incorporating the organoaluminum compound into the contacting-treated product of the step (2) , or by incorporating the contacting-treated product of the step (2) and organoaluminum compound into the saturated aliphatic hydrocarbon compound.
  • the contacting treatment temperature for the step (3) is preferably 7O 0 C or lower, more preferably 60°C or lower. It is also preferably 10°C or higher viewed from efficiently expressing the preliminary polymerization activity, more preferably 20 0 C or higher.
  • the contacting treatment time is normally 0.01 to 0.5 hours .
  • the contacting treatment in the step (3) is carried out preferably in the presence of an olefin, which is normally one used as a raw material for the preliminary polymerization.
  • Quantity of the olefin is preferably 0.05 to 1 g per 1 g of the solid promoter component .
  • the steps (1) to (3) may be carried out totally in the same preliminary polymerization reactor by incorporating the saturated aliphatic hydrocarbon compound, metallocene-base complex, solid promoter component and organoaluminum compound as the component (C) separately.
  • the steps (2) and (3) may be carried out in a preliminary polymerization reactor, or the step (3) may be carried out in a preliminary polymerization reactor.
  • an olefin is preliminarily polymerized in the presence of a preliminary polymerization catalyst to produce a preliminary polymerization catalyst component (X) .
  • the preliminary polymerization is carried out normally by slurry polymerization, which may be a batchwise, semi- batchwoise or continuous process. Moreover, it may be carried out in the presence of a chain transfer agent, e.g., hydrogen.
  • a chain transfer agent e.g., hydrogen
  • Slurry polymerization when adopted for the preliminary polymerization, is carried out in the presence of a solvent, which is normally a saturated aliphatic hydrocarbon compound, e.g., propane, n- butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane or heptane. They may be used either individually or in combination.
  • the compound preferably has a boiling point of 100°C or lower at normal pressure, more preferably 90°C or lower.
  • propane, n-butane, isobutane, n- pentane, isopentane, n-hexane and cyclohexane are more preferable .
  • Slurry polymerization when adopted for the preliminary polymerization, is carried out normally at a slurry concentration of 0.1 to 600 g of the solid promoter component per 1 L of the solvent, preferably 0.5 to 300 g/L.
  • the preliminary polymerization temperature is 65°C or less, preferably 60 0 C or less, more preferably 55 0 C or less from the viewpoint of enhancing a polymerization activity.
  • the preliminary polymerization temperature is normally -20 0 C or more, preferably 0°C or more, more preferably 10 0 C or more, still more preferably 2O 0 C or more.
  • the olefin partial pressure in the vapor phase of the preliminary polymerization is normally 0.001 to 2 MPa, preferably 0.01 to 1 MPa.
  • the polymerization time is normally 2 minutes to 15 hours.
  • the olefins useful for the preliminary polymerization include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclopentene and cyclohexene. They may be used either individually or in combination.
  • the olefin is only ethylene or a combination of ethylene and an ⁇ - olefin. More preferably, it is only ethylene, or a combination of ethylene and at least one species of ⁇ - olefin selected from the group consisting of 1-butene, 1-hexene and 1-octene.
  • the preliminary polymerization catalyst component (X) contains the polymer produced by the preliminary polymerization normally at 0.01 to 1000 g per 1 g of the solid promoter component, preferably 0.05 to 500 g/g, more preferably 0.1 to 200 g/g.
  • the step (II) for the present invention polymerizes an olefin in the presence of a polymerization catalyst prepared by bringing the preliminary polymerization catalyst component (X) into contact with an organoaluminum compound as the component (D) , represented by the general formula R 2 3 A1 (wherein, R 2 is a branched hydrocarbon group of 3 to 8 carbon atoms, wherein the R 2 may be the same or different) .
  • the organoaluminum compound as the component (D) is represented by the general formula R 2 3 A1 (wherein, R 2 is a branched hydrocarbon group of 3 to 8 carbon atoms, wherein the R 2 S may be the same or different) .
  • R 2 is a branched hydrocarbon group of 3 to 8 carbon atoms, wherein the R 2 S may be the same or different.
  • R 2 isobutyl, sec-butyl, neopentyl, isopentyl, 2-methylpentyl
  • the organoaluminum compounds for the component (D) tri(2- methylpentyl) aluminum and triisobutyl aluminum can be cited, of which triisobutyl aluminum is more preferable.
  • the molar ratio of the organoaluminum compound as the component (D) to be contacted in the step (II) is 1 to 10,000 as (Al/M) , wherein Al is aluminum in the organoaluminum compound and M is a transition metal derived from the metallocene-base complex, preferably 1 to 5,000.
  • Al aluminum in the organoaluminum compound
  • M is a transition metal derived from the metallocene-base complex
  • an organoaluminum compound other than the component (D) may be present.
  • the component (D) preferably accounts for 80% by mol or more based on the total organoaluminum compounds used in the step (II) , more preferably 90% by mol or more, from the viewpoint of enhancing a polymerization activity.
  • an electron donating compound may be used as a component (E) , as required.
  • the preferable electron donating compounds for the component (E) triethylamine and tri-n-oxtylamine can be cited.
  • Quantity of the electron donating compound as the component (E) is preferably 0.1% by mol or more based on aluminum for the component (D) , more preferably 1% by mol or more. It is also preferably 10% by mol or less viewed from enhancing the polymerization activity.
  • Polymerization for the step (II) is preferably slurry or vapor-phase polymerization.
  • a vapor-phase polymerization reactor for the vapor-phase polymerization normally has a fluidized bed type reaction tank, preferably having an expanded section. It may be equipped with a blade-type agitator in the reactor.
  • the preliminary polymerization catalyst component (X) may be supplied to a polymerization reaction tank normally by being carried by an inert gas (e.g., nitrogen or argon), hydrogen, ethylene or the like in the absence of moisture, or in the form of a solution or slurry with each of the components being dissolved in or diluted with a solvent.
  • an inert gas e.g., nitrogen or argon
  • hydrogen e.g., hydrogen, ethylene or the like in the absence of moisture, or in the form of a solution or slurry with each of the components being dissolved in or diluted with a solvent.
  • the polymerization temperature in the step (II) is normally below melting point of the olefin polymer, preferably 0 to 150°C, more preferably 30 to 100°C. It is also preferably below 90 0 C, more specifically 70 to 87°C.
  • the polymerization may be carried out in the presence of hydrogen working as a molecular weight adjustor for adjusting melting/flowability characteristics of the olefin polymer.
  • An inert gas may be present in the gas mixture .
  • ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4- methyl-1-pentene, cyclopentene and cyclohexene can be cited. They may be used either individually or in combination.
  • the olefin is only ethylene or a combination of ethylene and an ⁇ -olefin. More preferably, it is only ethylene, or a combination of ethylene and at least one species of ⁇ -olefin selected from the group consisting of 1-butene, 1-hexene and 1- octene .
  • the olefin polymer produced by the present invention is preferably an ethylene/ ⁇ -olefin copolymer.
  • ethylene/propylene, ethylene/1- butene, ethylene/1-hexene and ethylene/l-octene copolymers can be cited, of which ethylene/1-butene, ethylene/1-hexene and ethylene/1-butene/l-octene copolymers are more preferable .
  • the olefin polymer produced by the present invention may be incorporated, as required, with one or more known additives, e.g., foaming agent, foaming aid, cross-linking agent, cross-linking aid, oxidation inhibitor, antiweatherability agent, lubricant, antiblocking agent, antistatic agent, anti-fog additive, antidroplet agent, pigment, filler and so forth.
  • foaming agent foaming aid
  • cross-linking agent e.g., cross-linking agent
  • cross-linking aid e.g., oxidation inhibitor, antiweatherability agent, lubricant, antiblocking agent, antistatic agent, anti-fog additive, antidroplet agent, pigment, filler and so forth.
  • additives e.g., foaming agent, foaming aid, cross-linking agent, cross-linking aid, oxidation inhibitor, antiweatherability agent, lubricant, antiblocking agent, antistatic agent, anti-fog additive, antidroplet agent, pigment, filler and so
  • the olefin polymer produced by the present invention may be molded by a known method, e.g., extrusion molding (inflation or T-die film molding) , injection molding, compression molding or the like. Extrusion foaming molding, foaming molding at normal pressure or elevated pressure, or the like may be also employed. [0094]
  • the olefin polymer produced by the present invention may be molded into a shape by the above methods .
  • the molded shapes can find use in pipes/tubes, containers, caps, films, sheets and so forth.
  • they may be foamed in the form of single- or multi-layer structure, suitable for footwear mid-soles, outer soles or insoles for shoes, sandals and so forth.
  • Construction materials e.g., insulation materials, cushioning materials and so forth are other areas they can go into.
  • Example 1 Preparation of solid co-catalyst component
  • a reactor equipped with a stirrer was charged with 2.8 kg of silica (Davison, Sylopol948, 50% volume- average particle diameter: 55 ⁇ m, pore volume: 1.67 mL/g, specific surface area: 325 m 2 /g) and 24 kg of toluene, both heated at 300°C in a flow of nitrogen, after the reactor was purged with nitrogen, and the mixture was stirred. It was cooled to 5°C, and then incorporated with a mixed solution of 0.9 kg of 1, 1, 1, 3 , 3 , 3-hexamethyldisilazane and 1.4 kg of toluene dropwise in 30 minutes while the reactor was kept at 5 0 C, at which the resulting mixture was stirred for 1 hour.
  • silica Davison, Sylopol948, 50% volume- average particle diameter: 55 ⁇ m, pore volume: 1.67 mL/g, specific surface area: 325 m 2 /g
  • the gas composition in the system contained hydrogen at 1.9% by mol, determined by gas chromatography.
  • the gas composition in the system contained hydrogen at 1.6% by mol, determined by gas chromatography.
  • the autoclave was then charged with 2 mL of a 1 mmol/mL hexane solution of triisobutyl aluminum, and then with 1 mL of a 0.1 mmols/mL hexane solution of triethylamine . It was then charged with 88.5 mg of the preliminary polymerization catalyst component produced in the step (1) in Example 3.
  • the polymerization was carried out at 70°C while an ethylene/hydrogen mixed gas (hydrogen concentration: 0.42% by mol) was continuously supplied to keep the total pressure and hydrogen partial pressure constant .
  • the polymerization activity was 8355 g per 1 g of the solid promoter component (a) , after the polymerization was carried out for 1 hour.
  • the gas composition in the system contained hydrogen at 1.6% by mol, determined by gas chromatography.
  • the autoclave was then charged with 2 mL of a 1 mmol/mL hexane solution of triisobutyl aluminum, and then with 1 mL of a 0.1 mmols/mL hexane solution of triethylamine . It was then charged with 100 mg of the preliminary polymerization catalyst component produced in the step (1) in Comparative
  • Example 1 The polymerization was carried out at 70 0 C while an ethylene/hydrogen mixed gas (hydrogen concentration: 0.43% by mol) was continuously supplied to keep the total pressure and hydrogen partial pressure constant. The polymerization activity was 2074 g per 1 g of the solid promoter component (a) , after the polymerization was carried out for 1 hour. [0108] Comparative Example 2 (1) Preparation of preliminary polymerization catalyst component
  • the gas composition in the system contained hydrogen at 1.8% by mol, determined by gas chromatography.
  • the autoclave was then charged with 2 mli of a 1 mmol/mL hexane solution of triisobutyl aluminum, and then with 1 mL of a 0.1 mmol/mL hexane solution of triethylamine .
  • Comparative Example 3 (1) Production of ethylene/oc-olefin copolymer A 5 L autoclave equipped with a stirrer, dried under a vacuum, was charged with hydrogen while it was kept under a vacuum to a hydrogen partial pressure of 0.03 MPa, and then with 135 g of 1-hexene and 1066 g of butane. It was then charged with ethylene to its partial pressure of 1.6 MPa after the system temperature was increased to 70°C, to stabilize the system. The gas composition in the system contained hydrogen at 1.8% by mol, determined by gas chromatography.
  • the gas composition in the system contained hydrogen at 1.8% by mol, determined by gas chromatography.
  • the autoclave was then charged with 2 mL of a 1 mmol/mL hexane solution of triethyl aluminum, and then with 1 mL of a 0.1 mmol/mL hexane solution of triethylamine .
  • the present invention can provide a production process of olefin polymer, high in polymerization activity, and carried out in the presence of a metallocene-base catalyst.

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Abstract

La présente invention concerne un procédé très actif pour produire un polymère oléfinique qui comporte : l'étape (I) consistant à polymériser de manière préliminaire une oléfine à 65°C ou moins en présence d'un catalyseur de polymérisation préliminaire préparé en amenant les composants suivants (A), (B) et (C) en contact les uns avec les autres, pour produire un composant de catalyseur de polymérisation préliminaire (X) ; et l'étape (II) consistant à polymériser une oléfine en présence d'un catalyseur de polymérisation préparé en amenant le composant de catalyseur de polymérisation préliminaire (X) en contact avec le composant suivant (D), afin de produire un polymère oléfinique. Le composant (A) est un complexe à base de métallocène, le composant (B) est un composant co-catalytique solide dans lequel un composé capable d'ioniser le complexe à base de métallocène en un complexe ionique est porté sur un support de particules mince, le composant (C) est un composé d'organo-aluminium représenté par la formule générale R13Al (dans laquelle, R1 est un groupe hydrocarbure linéaire ayant de 1 à 8 atomes de carbone, dans lequel R1 peut être identique ou différent) et le composant(D) est un composé d'organo-aluminium représenté par la formule générale R23Al (dans laquelle, R2 est un groupe hydrocarbure ramifié ayant de 3 à 8 atomes de carbone, R2 pouvant être identique ou différent).
PCT/JP2008/053709 2007-02-26 2008-02-25 Procédé de production de polymère oléfinique WO2008105546A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9895811B2 (en) 2008-02-19 2018-02-20 Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Reno Targets and processes for fabricating same
CN110330582A (zh) * 2014-02-11 2019-10-15 尤尼威蒂恩技术有限责任公司 制造聚烯烃产物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002022693A1 (fr) * 2000-09-13 2002-03-21 Japan Polychem Corporation Catalyseur pour polymerisation d'olefines
JP2002293817A (ja) * 2001-03-30 2002-10-09 Sumitomo Chem Co Ltd 予備重合済オレフィン重合用触媒成分、オレフィン重合用触媒、およびオレフィン重合体の製造方法
JP2003292514A (ja) * 2002-03-29 2003-10-15 Sumitomo Chem Co Ltd 予備重合済オレフィン重合用触媒およびオレフィン重合体の製造方法
JP2004002764A (ja) * 2002-03-29 2004-01-08 Sumitomo Chem Co Ltd 予備重合済オレフィン重合用触媒およびオレフィン重合体の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002022693A1 (fr) * 2000-09-13 2002-03-21 Japan Polychem Corporation Catalyseur pour polymerisation d'olefines
JP2002293817A (ja) * 2001-03-30 2002-10-09 Sumitomo Chem Co Ltd 予備重合済オレフィン重合用触媒成分、オレフィン重合用触媒、およびオレフィン重合体の製造方法
JP2003292514A (ja) * 2002-03-29 2003-10-15 Sumitomo Chem Co Ltd 予備重合済オレフィン重合用触媒およびオレフィン重合体の製造方法
JP2004002764A (ja) * 2002-03-29 2004-01-08 Sumitomo Chem Co Ltd 予備重合済オレフィン重合用触媒およびオレフィン重合体の製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9895811B2 (en) 2008-02-19 2018-02-20 Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Reno Targets and processes for fabricating same
CN110330582A (zh) * 2014-02-11 2019-10-15 尤尼威蒂恩技术有限责任公司 制造聚烯烃产物
CN110330582B (zh) * 2014-02-11 2022-04-12 尤尼威蒂恩技术有限责任公司 制造聚烯烃产物

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