WO2001047635A2 - Geträgertes katalysatorsystem enthaltend ein metallocen, eine lewis-base und eine elementorganische verbindung der iii. hauptgruppe, sowie dessen verwendung - Google Patents

Geträgertes katalysatorsystem enthaltend ein metallocen, eine lewis-base und eine elementorganische verbindung der iii. hauptgruppe, sowie dessen verwendung Download PDF

Info

Publication number
WO2001047635A2
WO2001047635A2 PCT/EP2000/012641 EP0012641W WO0147635A2 WO 2001047635 A2 WO2001047635 A2 WO 2001047635A2 EP 0012641 W EP0012641 W EP 0012641W WO 0147635 A2 WO0147635 A2 WO 0147635A2
Authority
WO
WIPO (PCT)
Prior art keywords
amine
methyl
ethyl
catalyst system
indenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2000/012641
Other languages
German (de)
English (en)
French (fr)
Other versions
WO2001047635A3 (de
Inventor
Roland Kratzer
Cornelia Fritze
Jörg SCHOTTEK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Polyolefine GmbH
Original Assignee
Basell Polypropylen GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to EP00983307A priority Critical patent/EP1280600B1/de
Priority to DE50007414T priority patent/DE50007414D1/de
Priority to AT00983307T priority patent/ATE273071T1/de
Priority to US10/168,646 priority patent/US6953829B2/en
Priority to BRPI0016725-8A priority patent/BR0016725B1/pt
Priority to JP2001548219A priority patent/JP2003528167A/ja
Application filed by Basell Polypropylen GmbH filed Critical Basell Polypropylen GmbH
Priority to KR1020027008189A priority patent/KR20020081232A/ko
Priority to AU20091/01A priority patent/AU2009101A/en
Publication of WO2001047635A2 publication Critical patent/WO2001047635A2/de
Anticipated expiration legal-status Critical
Publication of WO2001047635A3 publication Critical patent/WO2001047635A3/de
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
    • 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
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/49—Hafnium
    • 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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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 catalyst system comprising at least one metallocene, at least one cocatalyst, at least one support material and optionally further organometallic compounds.
  • the catalyst system can advantageously be used for the polymerization of olefins, it being possible to dispense with the use of aluminoxanes, such as methylaluminoxane (MAO), which usually has to be used in large excess, as cocatalyst and nevertheless achieve high catalyst activity and good polymer morphology. It also avoids the use of ingredients that could be potentially toxic.
  • aluminoxanes such as methylaluminoxane (MAO)
  • MAO methylaluminoxane
  • metallocene catalysts require heterogenization of the catalyst system in order to ensure an appropriate morphology of the resulting polymer. It proves to be advantageous to covalently bind components of the catalyst system to the support in order to avoid the "bleeding" of the active component from the support and thus the deterioration of the polymer morphology.
  • the object of the present invention was to provide a catalyst system based on the covalent support of a cocatalyst which avoids the disadvantages of the prior art. Based on a special class of toxicologically harmless Lewis bases, a catalyst system was developed that unexpectedly enables high polymerization activities and good polymer morphology.
  • the catalyst system according to the invention contains
  • M 1 represents an element of the 5th main group of the Periodic Table of the Elements
  • R 1 , R 2 and R 3 are the same or different and for a hydrogen atom, a -C-C ( -, - alkyl, -C-C 2 o-haloalkyl, C 6 ⁇ C o-aryl, C 6 -C are o-haloaryl, C 7 -C o -alkylaryl or C 7 -C o-arylalkyl groups, where two or all three radicals R 1 , R 2 and R 3 are optionally substituted by C -C 2 o -ohlstoff - fineness can be linked to one another, at least one radical R 1 , R 2 or R 3 not representing a hydrogen atom or a linear alkyl chain and the compounds methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, triethylamine, triethylamine, tripropylamine , Tributylamine, N, N-dimethylaniline, N, N
  • R 4 and R 5 are the same or different and a hydrogen atom, a halogen atom, a C 1 -C 4 o-carbon-containing group, in particular C 1 -C 20 alkyl, C 1 -C o -haloalkyl, C 1 -C 1 alkoxy, C 6 -C 20 aryl, C 6 -C 20 haloaryl, C 6 -C 20 aryloxy, C 7 -C 40 arylalkyl, C -C 4 o-haloarylalkyl, C -C 4 o-alkylaryl, C 7 -C 4 o-haloalkylaryl, or R 4 is a -OSiR 3 group, in which R are identical or different and have the same meaning as R 5 ,
  • M 2 is the same or different and for an element of III.
  • Main group of the periodic table of the elements stands and
  • a, b and c each represent an integer 0, 1, 2 or 3 and a + b + c is not 0, is built up and is covalently bound to the support,
  • M 3 is an element of I., II. And III. Main group of the periodic table of the elements is
  • R 6 is the same or different and is a hydrogen atom, a halogen atom, a C ⁇ -C 4 o carbon-containing group, in particular C ⁇ -C 20 - alkyl, C 6 -C 4 o-aryl, C -C 4 o-aryl means alkyl or C -C 4 o-alkyl-aryl group,
  • d is an integer from 1 to 3 and
  • Lewis bases are preferably of the formula (I) wherein R 1, R 2 and R 3 are identical or different and represent a hydrogen atom, a C ⁇ -C2o-alkyl, C ⁇ -C 2 o-haloalkyl, C 6 -C 4 o-aryl, C 6 -C 40 -halo-aryl, C 7 -C 4 o-alkylaryl or C 7 -C 40 -arylalkyl group, where optionally two radicals or all three radicals R 1 , R 2 and R 3 can be connected to one another via C -C 2 o _ carbon units and wherein at least one radical R 1 , R 2 or R 3 represents a radical having 2 to 20 carbon atoms of the aromatic groups, which may optionally be substituted, and / or heteroatoms selected from the group P, O, S, N, may be. At least one radical R 1 , R 2 or R 3 preferably represents an alkyl aryl group, in particular a benzyl group, or a
  • N-benzylethylenediamine N-benzylisopropylamine, N-benzylmethylamine, N-benzylethylamine, N-benzyl-1-phenylethylamine, N-benzyl-2-phenylethylamine, or N-benzylpiperazine
  • N-methyl-N-ethyl-4-heptylamine N-methyl-N-ethyl-2-methylhexylamine N-methyl-N-ethyl-3-methylhexylamine, N-methyl-N-ethyl-4-methylhexylamine, N -Methyl-N-ethyl-5-methylhexylamine, N-methyl-N-ethyl-2-ethylpentylamine, N-methyl-N-ethyl-3-ethylpentylamine, N-methyl-N-ethyl-2-propylbutylamine, N-methyl -N-ethyl-cycloheptylamine, N-methyl-N-ethyl-methylcyclohexylamine, N-methyl-N-ethyl-benzylamine, N-methyl-N-ethyl-2-octylamine, N-methyl-N-ethyl-3-oc tylamine
  • N-methyl-dibenzylamine N-methyl-bis (2-octyl) amine, N-methyl-bis (3-octyl) amine
  • N-methyl-bis (4-octyl) amine N-methyl-bis (2-methylheptyl) amine, N-methyl-bis (3-methylheptyl) amine, N-methyl-bis (4-methylheptyl) amine, N- Methyl bis (5-methylhep yl) amine, N-methyl-bis (6-methylheptyl) amine, N-methyl-bis (2-ethylhexyl) amine, N-methyl-bis (3-ethylhexyl) amine , N-methyl-bis (4-ethylhexyl) amine, N-methyl-bis (2-propyl-pentyDamine, N-methyl-bis (cyclooctyl) amine, N-methyl-bis (dimethyl-cyclohexyl) amine, N-ethyl diisopropylamine, N-ethyl-bis (2-butyl) amine, N-ethyl-bis (isobuty
  • Particularly preferred bases are, for example, benzylamine, i ⁇ 7-benzyldimethylamine, N-benzyldiethylamine, W-benzylbutylamine, N-benzyl tert. -bu tylamine, N '-Benzyl-i ⁇ N-dimethylethylenediamine, IV-benzyl - thylenediamine, N-benzylisopropylamine, IV-benzylmethylamine, N-benzylethylamine, i ⁇ 7-benzyl-1-phenylethylamine, N-benzyl-2 -phenyl - ethylamine, or N-benzylpiperazine.
  • the carrier is a porous inorganic or organic solid.
  • the carrier preferably contains at least one inorganic oxide, such as silicon oxide, aluminum oxide, aluminosilicates, zeolites, MgO, Zr0 2 , Ti0 2 , B 2 0 3 , CaO, ZnO, Th0 2 , Na 2 C0 3 , K 2 C0 3 , CaC0 3 , MgCl 2 , Na 2 S0 4 , A1 2 (S0 4 ) 3 , BaS0 4 , KN0 3 , Mg (N0 3 ) 2 , A1 (N0 3 ) 3 , Na 2 0, K 2 0, Li 2 0, or Mixed oxides, in particular silicon oxide and / or aluminum oxide and / or Mg / Al mixed oxide.
  • inorganic oxide such as silicon oxide, aluminum oxide, aluminosilicates, zeolites, MgO, Zr0 2 , Ti0 2 , B 2 0 3 , CaO,
  • the carrier can also contain at least one polymer, for example a homo- or copolymer, a crosslinked polymer or polymer blends.
  • polymers are polyethylene, polypropylene, polybutene, polystyrene, polystyrene crosslinked with divinylbenzene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, polyamide, polymethacrylate, polycarbonate, polyester, polyacetal or polyvinyl alcohol.
  • the carrier has a specific surface area in the range from 10 to 1000 m 2 / g, preferably from 150 to 500 m 2 / g.
  • the average particle size of the carrier is 1 to 500 ⁇ m, preferably 5 to 350 ⁇ m, particularly preferably 10 to 200 ⁇ m.
  • the carrier is preferably porous with a pore volume of the carrier of 0.5 to 4.0 ml / g, preferably 1.0 to 3.5 ml / g.
  • a porous carrier has a certain proportion of voids (pore volume).
  • the shape of the pores is usually irregular, often spherical.
  • the pores can be connected to one another by small pore openings.
  • the pore diameter is preferably about 2 to 50 nm.
  • the particle shape of the porous carrier is dependent on the aftertreatment and can be irregular or spherical.
  • the particle size of the carrier can e.g. B. can be set arbitrarily by cryogenic grinding and / or sieving.
  • the catalyst system according to the invention contains as a cocatalytically active chemical compound at least one organic element compound which contains units of the formula (II).
  • Preferred compounds of the formula (II) are those in which M 2 is boron or aluminum.
  • the compound containing the formula (II) units can exist as a monomer or as a linear, cyclic or cage-like oligomer. It is also possible for two or more chemical compounds which contain units of the formula (II) to form interactions or condensation reactions with one another by means of Lewis acid-base, dinines, trimers or higher associates.
  • Preferred cocatalytically active elemental organic compounds according to d) correspond to the formulas (IV) and (V),
  • R 4 and R 5 have the same meaning as under formula (II).
  • compounds of the invention which are cocatalytically active are generally compounds which are formed by the reaction of at least one compound of the formula (VI) and / or (VII) and / or (VIII) with at least one compound of the formula (IX).
  • R 7 can be a hydrogen atom or a boron-free C 1 -C 40 carbon-containing group such as C 1 -C 6 alkyl, C 6 -C 0 aryl, C 7 -C 0 arylalkyl, C -C 4 o-alkylaryl and wherein wherein R 4 and R 5 have the same meaning as under formula (II).
  • X is an element of VI.
  • organometallic compounds of the formula (III) are preferably neutral Lewis acids in which M 4 is lithium, magnetic
  • organometallic compounds of the formula (III) are trimethyl aluminum, triethyl aluminum, tri-isopropyl aluminum, trihexyl aluminum, trioctyl aluminum, tri-n-butyl aluminum, tri-isobutyl aluminum, tri-n-propyl aluminum, triisoprene aluminum,
  • the metallocene compounds contained in the catalyst system according to the invention can be, for example, bridged or unbridged biscyclopentadienyl complexes, as described, for example, in EP-A-0,129,368, EP-A-0, 561, 79, EP-A-0, 545, 304 and EP- A-0, 576, 970, monocyclopentadienyl complexes, such as bridged amidocyclopentadienyl complexes, which are described, for example, in EP-A-0,416,815, multinuclear cyclopentadienyl complexes, such as, for example, described in EP-A-0, 632, 063, p-ligand-substituted tetrahydropentales described for example in EP-A-0,659,758 or ⁇ -ligand-substituted tetrahydroin
  • Organometallic compounds can also be used in which the complexing ligand does not contain a cyclopentadienyl ligand. Examples of this are diamine complexes of III. and IV. Subgroup of the Periodic Table of the Elements, as described, for example, in DH McConville, et al, Macromolecules, 1996, 29, 5241 and DH McConville, et al, J. Am. Chem. Soc, 1996, 118, 10008. Diimine complexes from Vlll. Subgroup of the Periodic Table of the Elements (eg Ni 2+ or Pd 2+ complexes), as described by Brookhart et al, J. Am. Chem. Soc.
  • Preferred metallocene compounds are unbridged or bridged compounds of the formula (X),
  • M 4 is a metal of III., IV., V. or VI. Subgroup of the periodic table of the elements, in particular Ti, Zr or Hf,
  • R 8 are the same or different and are a hydrogen atom or SiR 3 , in which R the same or different is a hydrogen atom or a C 1 -C 4 o -carbon-containing group such as C 1 -C 2 o -alkyl, C 1 -C 8 -fluoroalkyl, C ⁇ -C ⁇ o-alkoxy, C 6 -C 20 aryl, C 5 -C ⁇ o-fluoroaryl, C 6 -C ⁇ 0 -aryloxy, C 2 -C ⁇ o-alkenyl, C 7 -C 4 o-arylalkyl, C -C 4 o-alkylaryl or Cs-C 4 o-arylalkenyl, or R 8 are a -C-C 30 - carbon-containing group such as -C-C 25 ⁇ alkyl, z.
  • radicals R 8 can be linked together so that the radicals R 8 and the atoms of the cyclopentadienyl ring connecting them are carbon-containing or a form carbon and hetero atom-containing C -C 24 ring system, which in turn can be substituted,
  • R 9 are the same or different and are a hydrogen atom or SiR 3 , in which R is the same or different is a hydrogen atom or a -C-C 4 o-carbon-containing group such as -C-C 0 -alkyl, C ⁇ -C ⁇ o-fluoroalkyl, C ⁇ -C ⁇ o-alkoxy, Cg-C ⁇ aryl, C 6 -C ⁇ 0 -fluoroaryl, C 6 -C ⁇ 0 -aryloxy, C 2 -C ⁇ o-alkenyl, C 7 -C 4 o-arylalkyl, C -C 4th are o-alkylaryl or C 8 -C 40 arylalkenyl, or R 9 are a -C-C 30 - carbon-containing group such as -C-C 2 s-alkyl, for.
  • B methyl, ethyl, tert-butyl, cyclohexyl or octyl, C 2 -C 25 alkenyl, C 3 -C 5 alkylalkenyl, C 6 -C 24 aryl, C 5 -C 2 heteroaryl, e.g. , B.
  • radicals R 9 can be linked together so that the radicals R 9 and the atoms connecting them of the cyclopentadienyl ring are carbon-containing or carbon-containing and hetero-atom-containing C.
  • L 1 may be the same or different and are a hydrogen atom, a C ⁇ -C ⁇ 0 -hydrocarbon group such as C ⁇ -C ⁇ o-alkyl or C ⁇ -Cio-aryl, a halogen atom or OR 12, SR 12, OSiR 12 3, SiR 1: L 3 , PR 1: L or NR 1: L , wherein R 11 is a halogen atom, a CI-CIO alkyl group, a Ci-Cio alkoxy group, a halogenated Ci-Cio alkyl group, a C 6 -C 20 aryl group, C 7 -C 20 alkyl aryl group C 7 -C 0 aryl-alkyl group or a halogenated C 6 -C 0 aryl group, or L 1 are a toluenesulfonyl, trifluoracetyl, trifluoroacetoxyl, trifluoromethanesulfonyl, non
  • o is an integer from 1 to 4, preferably 2,
  • Z denotes a bridging structural element between the two cyclopentadienyl rings and v is 0 or 1.
  • Z examples are groups MR 10 R 1: L, where M is carbon, silicon zium, germanium or tin and R 10 and R 11 are the same or different, a C ⁇ -C o _ hydrocarbonaceous group, such as C ⁇ -C ⁇ o- l kyl, C 6 -C 4 aryl or trimethylsilyl mean.
  • Z is preferably CH 2 , CH 2 CH 2 , CH (CH 3 ) CH 2 , CH (C 4 H 9 ) C (CH 3 ) 2 , C (CH 3 ) 2 , (CH 3 ) 2 Si, (CH 3 ) 2 Ge, (CH 3 ) 2 Sn, (C 6 H 5 ) 2 Si, (C 6 H 5 ) (CH 3 ) Si, (C 6 H 5 ) 2 Ge, (C 6 H 5 ) 2 Sn , (CH 2 ) 4 Si, CH 2 Si (CH 3 ) 2 , oC 6 H 4 or 2, 2 '- (C 6 H 4 ) 2 .
  • Z can also form a mono- or polycyclic ring system with one or more radicals R 8 and / or R 9 .
  • Chiral bridged metallocene compounds of the formula (X) are preferred, in particular those in which v is 1 and one or both cyclopentadienyl rings are substituted in such a way that they contain an indenyl ring, a sulfur, nitrogen or oxygen-containing indenyl-analogous heterocycle or a sulfur, Represent nitrogen or oxygen-containing pentalen-analogous heterocycle.
  • Methyl (phenyl) silanediylbis (2-methyl-indenyl) zirconium dichloride Methyl (phenyl) silanediylbis (2-methyl-5-isobutyl-indenyl) zirconium dichloride 1, 2-ethanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride 1, 4 -Butanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride 1, 2-Ethanediylbis (2-methyl-4, 6 diisopropyl-indenyl) zirconium dichloride
  • Dimethylsilanediylbis (2-methyl-4- (4'-tert-butyl-phenyl-inde- nyl) zirconium dichloride.
  • Dimethylsilanediylbis (2-methyl-4- (4'-methyl-phenyl-indenyl) zirconium dichloride
  • Dimethylsilanediylbis (2-methyl-4- (4 '-trifluoromethyl-phenyl-inde- nyl) zirconium dichloride.
  • Dimethylsilanediylbis (2-methyl-4- (4'-methoxy-phenyl-indenyl) zirconium dichloride
  • Dimethylsilanediylbis (2-ethyl-4- (4'-tert-butyl-phenyl-indenyl) zirconium dichloride
  • Dimethylsilanediylbis (2-ethyl-4- (4 '-trifluoromethyl-phenyl-inde- nyl) zirconium dichloride.
  • Dimethylsilanediylbis (2-ethyl-4 * - (4'-methoxy-phenyl-indenyl) zirconium dichloride
  • Dimethylsilanediylbis (2-methyl-4- (4'-trifluoromethyl-phenyl-inde- nyl) zirconium dimethyl.
  • Dimethylsilanediylbis (2-methyl-4- (4 '-methoxy-phenyl-indenyl) zirconium dimethyl
  • Dimethylsilanediylbis (2-ethyl-4- (4'-trifluoromethyl-phenyl-inde- nyl) zirconium dimethyl.
  • Dimethylsilanediylbis (2-ethyl-4- (4 '-methoxy-phenyl-indenyl) zirconium dimethyl
  • Dimethylsilanediylbis (2-methyl-4- (4 '-trimethylsilyl-phenyl-inde- nyl) zirconium dimethyl)
  • Dimethylsilanediylbis (2-ethyl-4- (4' -trimethylsilyl-phenyl-inde- nyl) zirconium dichloride)
  • Dimethylsilanediylbis (2-methyl-4- (4 '-methyl-phenyl) -indenyl) zirconium dichloride Dimethylsilanediylbis (2-methyl-4- (4'-n-propyl-phenyl) -indenyl) zirconium dichloride
  • Dimethylsilanediylbis (2-hexyl-4-phenyl) -indenyl) zirconium dichloride Dimethylsilanediylbis (2-hexyl-4- (4 '-methyl-phenyl) -indenyl) zirconium dichloride
  • Ethylidenebis (2-ethyl-4- (4'-tert. -Butyl-phenyl) -indenyl) hafnium di-benzyl.
  • Ethylidenebis (2-ethyl-4- (4'-tert. -Butyl-phenyl) -indenyl) titanium dibenzyl
  • Methylethylidenebis (2-ethyl-4- (4'-tert.-butyl-phenyl) -indenyl) zirconium dichloride
  • Methylethylidenebis (2-ethyl-4- (4'-tert.-butyl-phenyl) -indenyl) hafnium dichloride
  • the catalyst system according to the invention can be obtained by reacting at least one Lewis base of the formula (I) and at least one elemental organic compound which is composed of units of the formula (II) with a support. The reaction is then carried out with a solution or suspension of one or more metallocene compounds of the formula (X) and optionally one or more organometallic compounds of the formula (III). This activation of the catalyst system can either be carried out before it is introduced into the reactor or can only be carried out in the reactor.
  • the support material is suspended in an organic solvent.
  • Suitable solvents are aromatic or aliphatic solvents such as hexane, heptane, toluene or xylene or halogenated hydrocarbons such as methylene chloride or halogenated aromatic hydrocarbons such as o-dichlorobenzene.
  • the amount of modified carrier for a metallocene compound of the formula (X) is preferably 10 g: 1 ⁇ mol to 10 -2 g: 1 ⁇ mol.
  • the stoichiometric ratio of metallocene compound of formula (X) to units of formula (II) from which the co-catalytic element geträ- siege to organic compound set ⁇ builds, is 100: 1 to 10 -4: 1, preferably 1: 1 to 10 " 2 : 1.
  • All of the reactions described for the preparation of the catalyst system according to the invention are preferably carried out in the temperature range from -40 to 110 ° C., particularly preferably from -10 ° C. to 70 ° C.
  • the supported catalyst system can be used directly for the polymerization. However, it can also be used resuspended for the polymerization after removal of the solvent.
  • the advantage of this activation method is that it offers the option of letting the polymerization-active catalyst system arise only in the reactor. This prevents partial decomposition when the air-sensitive catalyst is introduced.
  • the invention further relates to a process for producing an olefin polymer in the presence of the catalyst system according to the invention.
  • the polymerization can be a homo- or a copolymerization. Homopolymers or copolymers of polypropylene are preferably prepared.
  • olefins examples include 1-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, styrene, cyclic olefins such as norbornene, vinylnorbornene, tetracyclododecene, ethylidorbornene and dienes 1,3-butadiene or 1,4-hexadiene, biscyclopentadiene or methyl methacrylate.
  • 1-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, styrene, cyclic olefins such as norbornene, vinylnorbornene, tetracyclododecene, ethylidorbornene and dienes 1,3-butadiene or 1,4-hexadiene, biscyclopenta
  • propylene or ethylene are homopolymerized, ethylene with one or more C 3 -C 20 -1-olefins, in particular propylene, and / or one or more C 4 -C 20 -dienes, in particular 1, 3-butadiene, copolymerized or copolymerized norbornene and ethylene.
  • the polymerization is preferably carried out at a temperature of from -60 to 300.degree. C., particularly preferably from 30 to 250.degree.
  • the pressure is 0.5 to 2500 bar, preferably 2 to 1500 bar.
  • the polymerization can be carried out continuously or batchwise, in one or more stages, in solution, in suspension, in the gas phase or in a supercritical medium.
  • the supported catalyst system can either be formed directly in the polymerization system or it can be resuspended as a powder or solvent, and metered into the polymerization system as a suspension in an inert suspension medium.
  • a prepolymerization can be carried out with the aid of the catalyst system according to the invention.
  • the (or one of the) olefin (s) used in the polymerization is preferably used.
  • catalyst systems are preferably used which contain two or more different transition metal compounds, e.g. B. MetaUocene contain and / or two or more different cocatalytically active element organic compounds.
  • an aluminum alkyl for example trimethyl aluminum, triethyl aluminum or triisobutyl aluminum
  • This cleaning can take place both in the polymerization system itself or the olefin is brought into contact with the Al compound before the addition into the polymerization system and then separated again.
  • the total pressure in the polymerization system is 0.5 to 2500 bar, preferably 2 to 1500 bar.
  • the compound according to the invention is used in a concentration, based on the transition metal, of preferably 10 -3 to 10 ⁇ 8 , preferably 10 -4 to 10 ⁇ 7 mol, transition metal per dm 3 solvent or per dm 3 reactor volume.
  • Suitable solvents for the preparation of both the supported chemical compound according to the invention and the catalyst system according to the invention are aliphatic or aromatic solvents such as hexane or toluene, ethereal solvents such as tetrahydrofuran or diethyl ether or halogenated hydrocarbons such as methylene chloride or halogenated aromatic hydrocarbons such as o- dichlorobenzene.
  • an alkylaluminum compound such as trimethylaluminum, triethylaluminium, triisobutylaluminum, trioctylaluminium or isoprenylaluminium can be added to the reactor for inerting (for example to separate off existing catalyst poisons in the olefin). This is added to the polymerization system in a concentration of 200 to 0.001 mmol of AI per kg of reactor content.
  • Triisobutylaluminum and triethylaluminum are preferably used in a concentration of 10 to 0.01 mmol Al per kg reactor content, so that the molar Al / M 1 ratio can be chosen to be small in the synthesis of a supported catalyst system.
  • an additive such as an antistatic can be used in the process according to the invention, for example to improve the grain morphology of the olefin polymer.
  • antistatic agents that are suitable for the polymerization can be used. Examples of these are salt mixtures of calcium salts of medialanic acid and chromium salts of N-stearylanthranilic acid, which are described in DE-A-3, 543, 360.
  • suitable antistatic agents are, for example, isopropanol, C 2 to C fatty acid soaps from alkali or alkaline earth metals, salts of sulfonic acid esters, esters of polyethylene glycols with fatty acids, polyoxyethylene alkyl ethers, etc.
  • An overview of antistatic agents is given in EP-A-0, 107, 127.
  • a mixture of a metal salt of medialanic acid, a metal salt of anthranilic acid and a polyamine can be used as an antistatic, as described in EP-A-0, 636, 636.
  • the antistatic agent is used as a solution, are in the preferred case of isopropanol, Stadis ® 450 and Atmer 163 preferably 1 to 50 wt .-% of this solution, preferably 5 to 25 wt .-%, based on the weight of the supported catalyst used (carrier with covalently fixed metallocenium-forming compound and one or more metallocene compounds, for example of the formula (X), but the amounts of antistatic required can vary widely depending on the type of antistatic used.
  • the actual polymerization is preferably carried out in liquid monomer (bulk) or in the gas phase.
  • the antistatic can be metered in at any time for the polymerization.
  • a preferred procedure is that the supported catalyst system is resuspended in an organic solvent, preferably alkanes such as heptane or isododecane. It is then added to the polymerization autoclave with stirring. Then the antistatic is added. The polymerization is carried out at temperatures in the range from 0 to 100.degree.
  • a further preferred procedure is that the antistatic is metered into the polymerization autoclave before the supported catalyst system is added. The resuspended supported catalyst system is then metered in with stirring at temperatures in the range from 0 to 100.degree.
  • the polymerization time can range from 0.1 to 24 hours. A polymerization time in the range from 0.1 to 5 hours is preferred.
  • the polymers produced by the process according to the invention are distinguished by a narrow molecular weight distribution and good grain morphology.
  • Example 3 Reaction of tris (pentafluorophenyl) borane and bis (pentafluorophenyl) borinic acid with trimethyl aluminum
  • N, N-dimethylbenzylamine added. It is cooled to 0 ° C. and 50 ml of the solution prepared in Example 1 are added dropwise via a dropping funnel. The mixture is allowed to warm to room temperature and stirred for 3 hours. The suspension is then filtered and washed with pentane. The residue is then dried to constant weight in an oil pump vacuum. The result is 3.03 g of a white carrier material.
  • Example 6 Supporting the reaction mixture from Example 3
  • N, N-dimethylbenzylamine added. It is cooled to 0 ° C. and 40 ml of the solution prepared in Example 3 are added dropwise via a dropping funnel. The mixture is allowed to warm to room temperature and stirred for 3 hours. The suspension is then filtered and washed with pentane. The residue is then dried to constant weight in an oil pump vacuum. The result is 4.5 g of a white carrier material.
  • Example 4 0.5 g of the carrier prepared in Example 4 is added to 5.8 mg of dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) zirconium dimethyl (10 ⁇ mol) in 3 ml of toluene at room temperature. The suspension is stirred briefly and then 0.01 ml of trimethyl aluminum (TMA) (2M in toluene, 20 ⁇ mol) is added. The catalyst solution is stirred for 1 hour and then the solvent in Oil pump vacuum removed. The result is an orange-colored, free-flowing powder.
  • TMA trimethyl aluminum
  • Example 6 0.2 g of the carrier prepared in Example 6 are added to 3.3 mg of dimethylsilanediylbis (2-methyl-4- (4'-tert-butyl-phenyl-indenyl) zirconium dimethyl (5 ⁇ mol) in 3 ml of toluene at room temperature. The catalyst solution is stirred for 1 hour and then the solvent is stripped off in an oil pump vacuum, resulting in an orange-colored, free-flowing powder.
  • a dry 21 reactor is first flushed with nitrogen and then with propylene and filled with 1.5 l of liquid propylene. 3 ml of triisobutyl aluminum (TIBA) (20% in Varsol) are added and the mixture is stirred for 15 minutes.
  • the catalyst system 1 prepared in Example 7 is then injected resuspended in 20 ml of heptane and rinsed with 15 ml of heptane.
  • the reaction mixture is heated to the polymerization temperature of 60 ° C. and polymerized for 1 hour.
  • the polymerization is stopped by exhausting the remaining propylene.
  • the polymer is dried in a vacuum drying cabinet. The result is 160 g polypropylene powder (PP).
  • the reactor showed no deposits on the inner wall or stirrer.
  • the catalyst activity is 28 kg PP / g metallocene x h.
  • a dry 21 reactor is first flushed with nitrogen and then with propylene and filled with 1.5 l of liquid propylene. 3 ml of TIBA (20% in Varsol) are added and the mixture is stirred for 15 minutes. The catalyst system 3 prepared in Example 8 is then resuspended in 20 ml of heptane and rinsed with 15 ml of heptane. The reaction mixture is heated to the polymerization temperature of 60 ° C and 1 hour polymerized. The polymerization is stopped by exhausting the remaining propylene. The polymer is dried in a vacuum drying cabinet. The result is 255 g of polypropylene powder. The reactor showed no deposits on the inner wall or stirrer. The catalyst activity is 36 kg PP / g metallocene x h.
  • a dry 21 reactor is first flushed with nitrogen and then with propylene and filled with 1.5 l of liquid propylene. 3 ml of TIBA (20% in Varsol) are added and the mixture is stirred for 15 minutes. The catalyst system 3 prepared in Example 9 is then injected resuspended in 20 ml of heptane and rinsed with 15 ml of heptane. The reaction mixture is heated to the polymerization temperature of 60 ° C. and polymerized for 1 hour. The polymerization is stopped by exhausting the remaining propylene. The polymer is dried in a vacuum drying cabinet. The result is 145 g of polypropylene powder. The reactor showed no deposits on the inner wall or stirrer. The catalyst activity is 44 kg PP / g metallocene x h.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
PCT/EP2000/012641 1999-12-23 2000-12-13 Geträgertes katalysatorsystem enthaltend ein metallocen, eine lewis-base und eine elementorganische verbindung der iii. hauptgruppe, sowie dessen verwendung Ceased WO2001047635A2 (de)

Priority Applications (8)

Application Number Priority Date Filing Date Title
DE50007414T DE50007414D1 (de) 1999-12-23 2000-12-13 Geträgertes katalysatorsystem enthaltend ein metallocen, eine lewis-base und eine elementorganische verbindung der iii. hauptgruppe, sowie dessen verwendung
AT00983307T ATE273071T1 (de) 1999-12-23 2000-12-13 Geträgertes katalysatorsystem enthaltend ein metallocen, eine lewis-base und eine elementorganische verbindung der iii. hauptgruppe,sowie dessen verwendung
US10/168,646 US6953829B2 (en) 1999-12-23 2000-12-13 Catalyst system and the use thereof
BRPI0016725-8A BR0016725B1 (pt) 1999-12-23 2000-12-13 sistema catalisador compreendendo pelo menos um composto organometálico, pelo menos uma base de lewis, pelo menos um suporte e pelo menos um composto de organoelemento, uso do mesmo, e, processo para preparar poliolefinas.
JP2001548219A JP2003528167A (ja) 1999-12-23 2000-12-13 新規な触媒およびその使用法
EP00983307A EP1280600B1 (de) 1999-12-23 2000-12-13 Geträgertes katalysatorsystem enthaltend ein metallocen, eine lewis-base und eine elementorganische verbindung der iii. hauptgruppe, sowie dessen verwendung
KR1020027008189A KR20020081232A (ko) 1999-12-23 2000-12-13 신규한 촉매 시스템 및 이의 용도
AU20091/01A AU2009101A (en) 1999-12-23 2000-12-13 Novel catalyst system and the use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19962814.9 1999-12-23
DE19962814A DE19962814A1 (de) 1999-12-23 1999-12-23 Neues Katalysatorsystem und dessen Verwendung

Publications (2)

Publication Number Publication Date
WO2001047635A2 true WO2001047635A2 (de) 2001-07-05
WO2001047635A3 WO2001047635A3 (de) 2002-10-24

Family

ID=7934352

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/012641 Ceased WO2001047635A2 (de) 1999-12-23 2000-12-13 Geträgertes katalysatorsystem enthaltend ein metallocen, eine lewis-base und eine elementorganische verbindung der iii. hauptgruppe, sowie dessen verwendung

Country Status (11)

Country Link
US (1) US6953829B2 (enExample)
EP (1) EP1280600B1 (enExample)
JP (1) JP2003528167A (enExample)
KR (1) KR20020081232A (enExample)
CN (1) CN1177648C (enExample)
AT (1) ATE273071T1 (enExample)
AU (1) AU2009101A (enExample)
BR (1) BR0016725B1 (enExample)
DE (2) DE19962814A1 (enExample)
ES (1) ES2225280T3 (enExample)
WO (1) WO2001047635A2 (enExample)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004007570A3 (en) * 2002-07-15 2004-03-04 Basell Polyolefine Gmbh Preparation of supported catalyst systems
WO2004041871A1 (en) * 2002-11-04 2004-05-21 Basell Polyolefine Gmbh Preparation of catalyst compositions having improved activity
CN1319998C (zh) * 2002-11-04 2007-06-06 巴塞尔聚烯烃有限公司 具有提高的活性的催化剂组合物的制备
US7232869B2 (en) 2005-05-17 2007-06-19 Novolen Technology Holdings, C.V. Catalyst composition for olefin polymerization
WO2007039851A3 (en) * 2005-10-03 2008-05-22 Sasol Tech Pty Ltd Oligomerisation of olefinic compounds in the presence of an oligomerisation catalyst, and a catalyst activator including a halogenated organic group
US7569647B2 (en) 2002-10-10 2009-08-04 Basell Polyolefine Gmbh Process for the copolymerization of ethylene

Families Citing this family (98)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4571798B2 (ja) 2001-06-12 2010-10-27 バーゼル・ポリオレフィン・ゲーエムベーハー １−ブテンの重合方法
DE60233961D1 (de) 2001-06-12 2009-11-19 Basell Polyolefine Gmbh Verfahren zur Polymerisation von Buten-1
ATE321061T1 (de) 2001-06-22 2006-04-15 Basell Polyolefine Gmbh Metallocene, verwendung in katalysatoren für olefinpolymerisation
WO2003042258A1 (en) 2001-11-12 2003-05-22 Basell Polyolefine Gmbh Process for polymerizing 1-butene and 1-butene polymers
ES2268126T3 (es) 2001-11-30 2007-03-16 Basell Polyolefine Gmbh Compuestos de metaloceno y procedimiento para la preparacion de polimeros de propileno.
US7569648B2 (en) 2002-02-25 2009-08-04 Basell Polyolefine Gmbh Process for the copolymerization of ethylene
WO2004003072A1 (en) 2002-06-26 2004-01-08 Basell Poliolefine Italia S.P.A. Impact-resistant polyolefin compositions
US7700690B2 (en) 2002-06-26 2010-04-20 Basell Poliolefine Italia S.R.L. Impact-resistant polyolefin compositions
JP2005538198A (ja) 2002-09-06 2005-12-15 バセル ポリオレフィン ジーエムビーエイチ エチレンの共重合方法
US7534848B2 (en) 2002-12-04 2009-05-19 Basell Polyolefine Gmbh 1-butene copolymers and process for preparing them
US7589160B2 (en) 2002-12-04 2009-09-15 Basell Polyolefine Gmbh Process for preparing 1-butene polymers
US20070004814A1 (en) * 2003-04-17 2007-01-04 Basell Polyolefine Gmbh Process for preparing porous polymers and polymers thereof
RU2335504C2 (ru) 2003-05-08 2008-10-10 Базелль Полиолефине Гмбх Способ получения галогенидметаллоценовых соединений
KR101060985B1 (ko) * 2003-05-12 2011-08-31 바젤 폴리올레핀 게엠베하 1-부텐의 중합 방법
EP1648946B1 (en) 2003-07-04 2015-07-15 Basell Polyolefine GmbH Olefin polymerization process
JP2007505174A (ja) * 2003-09-11 2007-03-08 バセル ポリオレフィン ジーエムビーエイチ ヘテロ相プロピレンコポリマーを製造するための多段方法
BRPI0413961A (pt) * 2003-09-11 2006-10-31 Basell Polyolefine Gmbh processo multi-etapas para preparar copolìmeros heterofásicos de propileno
KR20060135607A (ko) * 2003-09-11 2006-12-29 바젤 폴리올레핀 게엠베하 헤테로페이스 프로필렌 공중합체의 제조를 위한 다단계공정
EP1664139A1 (en) * 2003-09-11 2006-06-07 Basell Polyolefine GmbH Multistep process for preparing heterophasic propylene copolymers
EP1518866A1 (en) * 2003-09-29 2005-03-30 Basell Poliolefine Italia S.P.A. Process for the preparation of porous ethylene polymers
EP1680468B1 (en) 2003-11-06 2011-08-17 Basell Poliolefine Italia S.r.l. Polypropylene composition
EP1697427B1 (en) 2003-12-22 2008-12-24 Basell Polyolefine GmbH Metallocene compounds
JP2005200503A (ja) * 2004-01-14 2005-07-28 National Institute Of Advanced Industrial & Technology プロピレンと共役ジエンとの共重合体及びその製造方法
DE602005023844D1 (de) 2004-03-12 2010-11-11 Basell Polyolefine Gmbh Verfahren zur polymerisation von 1-hexen oder höheren alpha-olefinen
EP1723184A1 (en) 2004-03-12 2006-11-22 Basell Polyolefine GmbH Process for polymerizing 1-hexene or higher alpha-olefins
ATE445650T1 (de) 2004-05-04 2009-10-15 Basell Polyolefine Gmbh Verfahren zur herstellung von ataktischen 1- butenpolymeren
JP4920587B2 (ja) 2004-06-08 2012-04-18 バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ 剛性、衝撃強さおよび破断点伸び率の良好なバランスならびに低い熱収縮を有するポリオレフィン組成物
JP5006783B2 (ja) 2004-07-13 2012-08-22 バーゼル・ポリオレフィン・ゲーエムベーハー メタロセン化合物、それらの調製で使用される配位子、１−ブテンポリマーの調製法、およびその方法から得られる１−ブテンポリマー
ATE388994T1 (de) 2004-07-22 2008-03-15 Basell Polyolefine Gmbh 1-butenpolymerzusammensetzung
CA2573984A1 (en) 2004-07-22 2006-01-26 Basell Polyolefine Gmbh Process for producing fractionable 1-butene polymers
AU2005296833A1 (en) 2004-10-18 2006-04-27 Basell Poliolefine Italia S.R.L. Butene-1 (co)polymers having low isotacticity
DE602005026837D1 (de) 2004-10-21 2011-04-21 Basell Polyolefine Gmbh 1-buten-polymer und herstellungsverfahren dafür
EP1655314A1 (en) 2004-11-09 2006-05-10 Basell Polyolefine GmbH Process for the preparation of 1-butene/propylene copolymers
KR20070093058A (ko) 2004-11-22 2007-09-17 바젤 폴리올레핀 게엠베하 프로필렌 기재 삼중합체
JP2008523231A (ja) * 2004-12-13 2008-07-03 バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ ポリオレフィン繊維
JP2008525651A (ja) * 2004-12-23 2008-07-17 バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ 弾性を有する繊維
EP1844099B1 (en) 2005-02-03 2011-03-16 Basell Polyolefine GmbH Process for producing thermoformed articles
EP1858907B1 (en) 2005-03-18 2008-10-15 Basell Polyolefine GmbH Metallocene compounds
JP2008536813A (ja) 2005-03-18 2008-09-11 バーゼル・ポリオレフィン・ゲーエムベーハー メタロセン化合物
AU2006226366A1 (en) 2005-03-23 2006-09-28 Basell Polyolefine Gmbh Process for the polymerizatio of olefins
EP1861435B1 (en) 2005-03-23 2016-01-13 Basell Polyolefine GmbH Process for the polymerization of olefins
US7964679B2 (en) 2005-05-03 2011-06-21 Basell Poliolefine Italia S.R.L. Process for the polymerization of alpha olefins
ATE515533T1 (de) 2005-05-11 2011-07-15 Basell Poliolefine Srl Polymerisationsverfahren zur herstellung von polyolefinblends
US8051611B2 (en) * 2005-06-24 2011-11-08 Dryvit Systems, Inc. Exterior insulation and finish system and method and tool for installing same
US20090234084A1 (en) * 2005-06-30 2009-09-17 Basell Polyolefine Gmbh Metallocene Compounds
WO2007045603A1 (en) 2005-10-21 2007-04-26 Basell Polyolefine Gmbh Propylene polymers
JP5379479B2 (ja) 2005-10-21 2013-12-25 バーゼル・ポリオレフィン・ゲーエムベーハー 射出成形用のポリプロピレン
EP1940888B1 (en) * 2005-10-21 2010-06-02 Basell Polyolefine GmbH Polypropylene random copolymers having high melt flow rates for injection molding and melt brown applications
EP1984407A2 (en) * 2006-01-11 2008-10-29 Ineos Europe Limited Supported catalyst system
CA2766253A1 (en) * 2006-02-02 2007-08-09 Basell Polyolefine Gmbh Propylene homopolymer melt blown resins
CA2643339A1 (en) 2006-02-23 2007-08-30 Basell Poliolefine Italia S.R.L. Propylene polymers for injection molding applications
JP2009530341A (ja) 2006-03-17 2009-08-27 バーゼル・ポリオレフィン・ゲーエムベーハー メタロセン化合物類
US7834205B2 (en) 2006-04-12 2010-11-16 Basell Polyolifine GmbH Metallocene compounds
US8785575B2 (en) 2006-04-21 2014-07-22 Basell Polyolefine Gmbh Process for the preparation of ethylene propylene copolymers
WO2007122098A1 (en) 2006-04-21 2007-11-01 Basell Polyolefine Gmbh Process for the preparation of ethylene copolymers
US8097681B2 (en) 2006-08-30 2012-01-17 Basell Polyolefine Gmbh 1-butene propylene copolymer compositions
EP2057226B1 (en) 2006-08-30 2009-12-09 Basell Polyolefine GmbH 1-butene propylene copolymer compositions
JP5039373B2 (ja) * 2006-12-13 2012-10-03 日本ポリエチレン株式会社 オレフィン重合用触媒成分の製造方法、オレフィン重合用触媒及びオレフィンの重合方法
US8058200B2 (en) * 2007-05-17 2011-11-15 Chevron Phillips Chemical Company, L.P. Catalysts for olefin polymerization
JP5306340B2 (ja) * 2007-06-25 2013-10-02 バーゼル・ポリオレフィン・ゲーエムベーハー １−ブテンエチレンコポリマー
WO2009050037A1 (en) * 2007-10-19 2009-04-23 Basell Polyolefine Gmbh Metallocene compounds based on ethanediyl-bridged indene and cyclopentadithiophene ligands
WO2009080438A1 (en) 2007-12-20 2009-07-02 Basell Polyolefine Gmbh Process for obtaining polymers of ethylene and cycloolefins
KR101580849B1 (ko) * 2008-02-29 2015-12-30 바셀 폴리올레핀 이탈리아 에스.알.엘 폴리올레핀 조성물
US20100324238A1 (en) * 2008-03-20 2010-12-23 Basell Poliolefine Italia S.R.L 1-butene terpolymers
US20100324244A1 (en) * 2008-03-20 2010-12-23 Basell Poliolefine Italia S.R.L. 1-butene copolymers
EP2254946B1 (en) * 2008-03-20 2012-02-01 Basell Poliolefine Italia S.r.l. Compositions of 1-butene based polymers
EP2254919A1 (en) * 2008-03-20 2010-12-01 Basell Poliolefine Italia S.R.L. 1-butene copolymers
WO2010003026A1 (en) * 2008-07-01 2010-01-07 The Regents Of The University Of Colorado Methods for extensive dark curing based on visible-light initiated, controlled radical polymerization
WO2010034684A2 (en) * 2008-09-24 2010-04-01 Basell Poliolefine Italia S.R.L. Polyolefin compositions having good resistance at whitening
EP2172493A1 (en) * 2008-10-02 2010-04-07 Total Petrochemicals Research Feluy Activating supports based on perfluorinated boronic acids
WO2010069775A1 (en) * 2008-12-19 2010-06-24 Basell Poliolefine Italia S.R.L. Polyolefin Fibres
EP2379609B1 (en) 2009-01-13 2012-10-24 Basell Polyolefine GmbH Polyethylene copolymers
US8802781B2 (en) 2009-01-13 2014-08-12 Basell Poliolefine Italia S.R.L. Polymer composition
WO2011061151A1 (en) 2009-11-17 2011-05-26 Basell Polyolefine Gmbh Ethylene copolymers
EP2606970A1 (en) 2011-12-19 2013-06-26 Basell Polyolefine GmbH Monocyclopentadienyl binuclear complexes, ligands used in their preparaion, catalyst systems comprising them and olefin polymerisation process
KR101549206B1 (ko) 2012-05-08 2015-09-02 주식회사 엘지화학 안사-메탈로센 화합물 및 이를 이용한 담지 촉매의 제조방법
EP2676972A1 (en) 2012-06-19 2013-12-25 Basell Polyolefine GmbH Process for the obtainment of a polyolefin composition
EP2743000A1 (en) 2012-12-13 2014-06-18 Basell Poliolefine Italia S.r.l. Catalyst system for the preparation of polyolefins
EP2767542A1 (en) 2013-02-18 2014-08-20 Basell Polyolefine GmbH Oligomerization catalyst
SG10201802959WA (en) 2013-07-17 2018-05-30 Exxonmobil Chemical Patents Inc Cyclopropyl substituted metallocene catalysts
US9938364B2 (en) 2013-07-17 2018-04-10 Exxonmobil Chemical Patents Inc. Substituted metallocene catalysts
US9458260B2 (en) 2013-07-17 2016-10-04 Exxonmobil Chemical Patents Inc. Process using substituted metallocene catalysts and products therefrom
WO2015009470A1 (en) 2013-07-17 2015-01-22 Exxonmobil Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
ES2715831T3 (es) 2013-07-17 2019-06-06 Exxonmobil Chemical Patents Inc Catalizadores de metaloceno sustituidos
US9644047B2 (en) 2013-07-17 2017-05-09 Exxonmobil Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
US10280235B2 (en) 2015-06-05 2019-05-07 Exxonmobil Chemical Patents Inc. Catalyst system containing high surface area supports and sequential polymerization to produce heterophasic polymers
US10280233B2 (en) 2015-06-05 2019-05-07 Exxonmobil Chemical Patents Inc. Catalyst systems and methods of making and using the same
US10294316B2 (en) 2015-06-05 2019-05-21 Exxonmobil Chemical Patents Inc. Silica supports with high aluminoxane loading capability
WO2016196331A1 (en) 2015-06-05 2016-12-08 Exxonmobil Chemical Patents Inc. Supported metallocene catalyst systems for polymerization
US9809664B2 (en) 2015-06-05 2017-11-07 Exxonmobil Chemical Patents Inc. Bimodal propylene polymers and sequential polymerization
US10329360B2 (en) 2015-06-05 2019-06-25 Exxonmobil Chemical Patents Inc. Catalyst system comprising supported alumoxane and unsupported alumoxane particles
CN107690441A (zh) 2015-06-05 2018-02-13 埃克森美孚化学专利公司 聚合物在气相或淤浆相中的单反应器制备
CN107922537B (zh) 2015-06-05 2021-07-27 埃克森美孚化学专利公司 气相或淤浆相中多相聚合物的制备
EP3464390A1 (en) 2016-05-27 2019-04-10 ExxonMobil Chemical Patents Inc. Metallocene catalyst compositions and polymerization process therewith
CN108570119B (zh) * 2017-03-10 2020-07-31 北京利和知信科技有限公司 一种含有萘二胺类化合物的固体催化剂组分、催化剂及其应用
US11518824B2 (en) 2017-10-11 2022-12-06 Basell Polyolefine Gmbh Supported catalyst system
US11472828B2 (en) 2019-10-11 2022-10-18 Exxonmobil Chemical Patents Inc. Indacene based metallocene catalysts useful in the production of propylene polymers
CN118401602A (zh) 2021-12-23 2024-07-26 巴塞尔聚烯烃意大利有限公司 软质聚烯烃组合物

Family Cites Families (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2059168A5 (en) * 1970-03-05 1971-05-28 Leuna Werke W Ulbr Cross-linking of ester-contg polymerisates
JPS5964604A (ja) 1982-10-06 1984-04-12 Sumitomo Chem Co Ltd ポリオレフインの製造方法
ZA844157B (en) 1983-06-06 1986-01-29 Exxon Research Engineering Co Process and catalyst for polyolefin density and molecular weight control
DE3543360A1 (de) 1985-12-07 1987-06-11 Erich Pfeiffer Verfahren zum herstellen von homo- und copolymerisaten des ethylens durch suspensionspolymerisation
IL85097A (en) 1987-01-30 1992-02-16 Exxon Chemical Patents Inc Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes
NZ235032A (en) 1989-08-31 1993-04-28 Dow Chemical Co Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component
ATE186918T1 (de) 1990-01-02 1999-12-15 Exxon Chemical Patents Inc Ionische metallocenkatalysatoren auf träger für olefinpolymerisation
TW309523B (enExample) 1991-11-30 1997-07-01 Hoechst Ag
TW294669B (enExample) 1992-06-27 1997-01-01 Hoechst Ag
US5449650A (en) * 1992-12-08 1995-09-12 Mitsubishi Petrochemical Company Limited Catalyst components for polymerization of olefins and use thereof
US5372980A (en) 1993-06-03 1994-12-13 Polysar Bimetallic metallocene alumoxane catalyst system and its use in the preparation of ethylene-alpha olefin and ethylene-alpha olefin-non-conjugated diolefin elastomers
DE4325824A1 (de) 1993-07-31 1995-02-02 Basf Ag Verfahren zur Herstellung von Homopolymerisaten des Ethylens oder Copolymerisaten des Ethylens
FI945959L (fi) 1993-12-21 1995-06-22 Hoechst Ag Metalloseenejä ja niiden käyttö katalyytteinä
FI945958L (fi) 1993-12-21 1995-06-22 Hoechst Ag Menetelmä polyolefiinien valmistamiseksi
FR2726563B1 (fr) * 1994-11-04 1996-12-13 Inst Francais Du Petrole Nouveaux composes du rhenium et de l'aluminium, leur preparation et leur utilisation en tant que catalyseurs
US5939347A (en) 1995-01-25 1999-08-17 W.R. Grace & Co. -Conn. Supported catalytic activator
US5726332A (en) * 1995-09-21 1998-03-10 Witco Gmbh Synthesis of novel organometallics and their use in olefin polymerization
JPH09302021A (ja) * 1996-03-13 1997-11-25 Mitsui Petrochem Ind Ltd オレフィン重合体の製造方法
DE19647070A1 (de) * 1996-11-14 1998-05-20 Hoechst Ag Geträgerte chemische Verbindung
DE19632557A1 (de) * 1996-08-13 1998-02-19 Hoechst Ag Chemische Verbindung
DE59703850D1 (de) 1996-08-13 2001-07-26 Basell Polyolefine Gmbh Geträgertes Katalysatorsystem, Verfahren zu seiner Herstellung und seine Verwendung zur Polymerisation von Olefinen
ID22443A (id) 1996-11-15 1999-10-14 Montelll Technology Co Bv Metallosena heterosiklik dan polimerisasi katalis
DE19744102A1 (de) 1997-10-06 1999-04-15 Targor Gmbh Katalysatorsystem
DE19804970A1 (de) * 1998-02-07 1999-08-12 Aventis Res & Tech Gmbh & Co Katalysatorsystem
TR200002404T2 (tr) 1998-02-20 2001-01-22 The Dow Chemical Company Genişletilmiş anyonlar ihtiva eden katalizör etkinleştiriciler
TW562810B (en) * 1998-04-16 2003-11-21 Mitsui Chemicals Inc Catalyst for olefinic polymerization and method for polymerizing olefine
DE19823171A1 (de) * 1998-05-23 1999-11-25 Aventis Res & Tech Gmbh & Co Verwendung eines Katalysatorsystems enthaltend Metallocene
DE19823172A1 (de) * 1998-05-23 1999-11-25 Aventis Res & Tech Gmbh & Co Katalysatorsystem und seine Verwendung zur Polymerisation von Propylen
DE19823168A1 (de) * 1998-05-23 1999-11-25 Aventis Res & Tech Gmbh & Co Katalysatorsystem
EP1082353B1 (de) * 1998-05-23 2006-02-22 Basell Polyolefine GmbH Katalysatorsystem und seine verwendung zur polymerisation von propylen
DE19828271A1 (de) * 1998-06-25 1999-12-30 Elenac Gmbh Verfahren zur Herstellung eines geträgerten Katalysatorsystems
WO2000011006A1 (en) * 1998-08-18 2000-03-02 The Dow Chemical Company Metalloid salt catalyst/activators
EP1074557A3 (de) * 1999-07-31 2003-02-26 Basell Polyolefine GmbH Übergangsmetallverbindung, Ligandensystem, Katalysatorsystem und seine Verwendung zur Polymerisation von Olefinen

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004007570A3 (en) * 2002-07-15 2004-03-04 Basell Polyolefine Gmbh Preparation of supported catalyst systems
US7618912B2 (en) 2002-07-15 2009-11-17 Basell Polyolefine Gmbh Preparation of supported catalyst systems
US7569647B2 (en) 2002-10-10 2009-08-04 Basell Polyolefine Gmbh Process for the copolymerization of ethylene
WO2004041871A1 (en) * 2002-11-04 2004-05-21 Basell Polyolefine Gmbh Preparation of catalyst compositions having improved activity
CN1319998C (zh) * 2002-11-04 2007-06-06 巴塞尔聚烯烃有限公司 具有提高的活性的催化剂组合物的制备
US7414005B2 (en) 2002-11-04 2008-08-19 Basell Polyolefine Gmbh Preparation of catalyst compositions having improved activity
US7232869B2 (en) 2005-05-17 2007-06-19 Novolen Technology Holdings, C.V. Catalyst composition for olefin polymerization
US7468416B2 (en) 2005-05-17 2008-12-23 Lummus Technology Inc. Catalyst composition for olefin polymerization
WO2007039851A3 (en) * 2005-10-03 2008-05-22 Sasol Tech Pty Ltd Oligomerisation of olefinic compounds in the presence of an oligomerisation catalyst, and a catalyst activator including a halogenated organic group
US8134038B2 (en) 2005-10-03 2012-03-13 Sasol Technology (Pty) Limited Oligomerisation of olefinic compounds in the presence of an oligomerisation catalyst, and a catalyst activator including a halogenated organic group

Also Published As

Publication number Publication date
DE19962814A1 (de) 2001-06-28
JP2003528167A (ja) 2003-09-24
ES2225280T3 (es) 2005-03-16
DE50007414D1 (de) 2004-09-16
EP1280600A2 (de) 2003-02-05
US6953829B2 (en) 2005-10-11
BR0016725B1 (pt) 2011-03-22
AU2009101A (en) 2001-07-09
KR20020081232A (ko) 2002-10-26
BR0016725A (pt) 2002-09-03
CN1177648C (zh) 2004-12-01
EP1280600B1 (de) 2004-08-11
CN1433339A (zh) 2003-07-30
US20030008984A1 (en) 2003-01-09
WO2001047635A3 (de) 2002-10-24
ATE273071T1 (de) 2004-08-15

Similar Documents

Publication Publication Date Title
EP1280600A2 (de) Geträgertes katalysatorsystem enthaltend ein metallocen, eine lewis-base und eine elementorganische verbindung der iii. hauptgruppe, sowie dessen verwendung
EP1175262B1 (de) Katalysatorsystem
EP1053263B1 (de) Katalysatorsystem
EP1042371B1 (de) Geträgertes katalysatorsystem zur polymerisation von olefinen
EP1250363B1 (de) Chemische verbindung, verfahren zu deren herstellung und deren verwendung in katalysatorsystemen zur herstellung von polyolefinen
EP1023334B1 (de) Katalysatorsystem
EP1290002B1 (de) Als cokatalysator geeignete chemische produkte, verfahren zu ihrer herstellung und ihre verwendung in katalysator-systemen zur herstellung von polyolefinen
EP1058694B1 (de) Katalysatorsystem, verfahren zu seiner herstellung und seine verwendung zur polymerisation von olefinen
EP1086146A1 (de) Katalysatorsystem
WO2001068718A1 (de) Salzartige chemische verbindung, verfahren zu deren herstellung und deren verwendung in katalysatorsystemen zur herstellung von polyolefinen
EP1084159B1 (de) Katalysatorsystem mit metallocenen mit fluorhaltigen substituenten
WO2000020466A9 (de) Katalysatorsystem
EP1334107A2 (de) Non-metallocene, verfahren zur herstellung von diesen und deren verwendung zur polymerisation von olefinen
EP1175424A1 (de) Chemische verbindung, verfahren zu deren herstellung und deren verwendung in katalysatorsystem zur herstellung von polyolefinen
DE19845240A1 (de) Katalysatorsystem
DE19817725A1 (de) Verwendung von Katalysatorsystemen enthaltend Metallocene mit fluorhaltigen Substituenten
DE19817726A1 (de) Katalysatorsystem mit Metallocenen mit fluorhaltigen Substituenten

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWE Wipo information: entry into national phase

Ref document number: 2000983307

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 1020027008189

Country of ref document: KR

ENP Entry into the national phase

Ref country code: JP

Ref document number: 2001 548219

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: 10168646

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 008185492

Country of ref document: CN

AK Designated states

Kind code of ref document: A3

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

WWP Wipo information: published in national office

Ref document number: 1020027008189

Country of ref document: KR

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 2000983307

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 2000983307

Country of ref document: EP