DE69801299T2 - Phyllosilikat-geträgerter Katalysator für die Olefinenpolymerisation - Google Patents

Phyllosilikat-geträgerter Katalysator für die Olefinenpolymerisation

Info

Publication number
DE69801299T2
DE69801299T2 DE69801299T DE69801299T DE69801299T2 DE 69801299 T2 DE69801299 T2 DE 69801299T2 DE 69801299 T DE69801299 T DE 69801299T DE 69801299 T DE69801299 T DE 69801299T DE 69801299 T2 DE69801299 T2 DE 69801299T2
Authority
DE
Germany
Prior art keywords
phyllosilicate
supported catalyst
olefin polymerization
olefin
polymerization
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.)
Expired - Lifetime
Application number
DE69801299T
Other languages
English (en)
Other versions
DE69801299D1 (de
Inventor
Takehiro Sagae
Yumito Uehara
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.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
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 claimed from JP31310497A external-priority patent/JPH11147905A/ja
Priority claimed from JP31310297A external-priority patent/JPH11147903A/ja
Priority claimed from JP31310397A external-priority patent/JP3945877B2/ja
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Publication of DE69801299D1 publication Critical patent/DE69801299D1/de
Application granted granted Critical
Publication of DE69801299T2 publication Critical patent/DE69801299T2/de
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • B01J31/02—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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • 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
    • B01J31/143—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 of aluminium
    • 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
    • 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
    • C08F4/02—Carriers therefor
    • C08F4/025—Metal oxides
    • 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
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • 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
    • 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
    • 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
    • B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
    • 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
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • 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
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/20—Non-coordinating groups comprising halogens
    • B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts
DE69801299T 1997-04-25 1998-04-24 Phyllosilikat-geträgerter Katalysator für die Olefinenpolymerisation Expired - Lifetime DE69801299T2 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP10917397 1997-04-25
JP31310497A JPH11147905A (ja) 1997-11-14 1997-11-14 エチレン重合体の製造方法およびエチレン重合体
JP31310297A JPH11147903A (ja) 1997-11-14 1997-11-14 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
JP31310397A JP3945877B2 (ja) 1997-11-14 1997-11-14 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

Publications (2)

Publication Number Publication Date
DE69801299D1 DE69801299D1 (de) 2001-09-13
DE69801299T2 true DE69801299T2 (de) 2002-04-18

Family

ID=27469699

Family Applications (1)

Application Number Title Priority Date Filing Date
DE69801299T Expired - Lifetime DE69801299T2 (de) 1997-04-25 1998-04-24 Phyllosilikat-geträgerter Katalysator für die Olefinenpolymerisation

Country Status (4)

Country Link
US (2) US6048817A (de)
EP (1) EP0874006B1 (de)
CN (1) CN1100798C (de)
DE (1) DE69801299T2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10314369A1 (de) * 2003-03-28 2004-10-14 Otto-Von-Guericke-Universität Magdeburg Polymerisationskatalysatoren auf Porenbetonbasis, Verfahren und ihre Herstellung und ihre Verwendung

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JP2000086717A (ja) * 1998-09-14 2000-03-28 Idemitsu Petrochem Co Ltd オレフィン又はスチレン類の重合用触媒及び重合体の製造方法
AU5279000A (en) * 1999-05-19 2000-12-05 National Institute Of Standards And Technology ("Nist") Polymer layered inorganic nanocomposites
US6559090B1 (en) 1999-11-01 2003-05-06 W. R. Grace & Co.-Conn. Metallocene and constrained geometry catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation
US6632911B1 (en) * 1999-11-05 2003-10-14 Japan Polychem Corporation Ethylene/α-olefin copolymer and film made thereof
CN1267191C (zh) * 1999-12-30 2006-08-02 菲利浦石油公司 有机金属催化剂组合物
CN1868583B (zh) * 1999-12-30 2013-06-05 菲利浦石油公司 有机金属催化剂组合物
KR100364491B1 (ko) * 2000-07-18 2002-12-12 삼성종합화학주식회사 신디오탁틱 폴리스티렌 나노컴포지트 및 그 제조방법
US7005400B2 (en) * 2001-04-05 2006-02-28 Japan Polychem Corporation Component of catalyst for polymerizing olefin, catalyst for polymerizing olefin and process for polymerizing olefin
KR100917529B1 (ko) * 2001-04-30 2009-09-16 더블유.알. 그레이스 앤드 캄파니-콘. 지지된 전이 금속 촉매 시스템의 제조 방법 및 그 방법에 의해 제조된 촉매 시스템
EP1401890B1 (de) * 2001-04-30 2010-12-15 W. R. Grace & Co.-Conn Chromträgeragglomerat-übergangsmetall-polymerisationskatalysatoren und verfahren, bei denen diese zur anwendung kommen
US6943224B2 (en) 2001-04-30 2005-09-13 W. R. Grace & Co.-Conn. Process for preparing supported transition metal catalyst systems and catalyst systems prepared thereby
WO2002088198A1 (en) * 2001-04-30 2002-11-07 W.R. Grace & Co.-Conn. Method of making supported transition metal polymerization catalysts and compositions formed therefrom
EP1399491B1 (de) * 2001-04-30 2006-08-23 W.R. Grace & Co.-Conn. Geträgerte dualübergangsmetallkatalysatorsysteme
EP1453868A2 (de) * 2001-04-30 2004-09-08 W. R. Grace & Co.-Conn Koordinationskatalysatorsysteme unter verwendung von chromträgeragglomerat und verfahren zu ihrer herstellung
KR100628620B1 (ko) 2001-04-30 2006-09-26 더블유.알. 그레이스 앤드 캄파니-콘. 이종 크롬 촉매 및 이를 사용하는 올레핀의 중합 방법
JP4110952B2 (ja) * 2002-01-16 2008-07-02 株式会社村田製作所 誘電体薄膜の形成方法
US20030236365A1 (en) * 2002-06-24 2003-12-25 Fina Technology, Inc. Polyolefin production with a high performance support for a metallocene catalyst system
US7244795B2 (en) * 2003-12-08 2007-07-17 Univation Technologies, Llc Polymerization process using metallocene catalyst systems
US7741417B2 (en) * 2004-01-07 2010-06-22 Exxonmobil Chemical Patents Inc. Preparation of polymerization catalyst activators utilizing indole-modified silica supports
US7220695B2 (en) * 2004-01-07 2007-05-22 Exxonmobil Chemical Patents Inc. Supported activator
US20080281139A1 (en) * 2005-02-10 2008-11-13 Mitsui Chemicals, Inc. Catalyst for Propylene Dimerization and Dimerization Method
US8022005B2 (en) 2007-11-08 2011-09-20 Exxonmobil Chemical Patents Inc. Halogen substituted heterocyclic heteroatom containing ligands-alumoxane activation of metallocenes
JP5308794B2 (ja) * 2007-12-11 2013-10-09 住友化学株式会社 噴流層装置を用いたポリオレフィン製造方法
JP5308797B2 (ja) * 2007-12-11 2013-10-09 住友化学株式会社 オレフィン重合反応装置、ポリオレフィン製造システム、及び、ポリオレフィン製造方法
JP5249730B2 (ja) * 2007-12-11 2013-07-31 住友化学株式会社 オレフィン重合反応装置及びポリオレフィン製造方法
JP5308795B2 (ja) * 2007-12-11 2013-10-09 住友化学株式会社 ポリオレフィン製造方法、並びに、噴流層装置を備えたポリオレフィン製造システム
JP5427396B2 (ja) * 2007-12-11 2014-02-26 住友化学株式会社 粉体移送装置、及び、ポリオレフィンの製造方法
JP5545800B2 (ja) * 2009-06-08 2014-07-09 住友化学株式会社 噴流−流動層型オレフィン重合反応装置、ポリオレフィン製造システム、及び、ポリオレフィン製造方法
US9751961B2 (en) * 2013-10-25 2017-09-05 Japan Polypropylene Corporation Catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for producing olefin (co)polymer using the same
US9321854B2 (en) 2013-10-29 2016-04-26 Exxonmobil Chemical Patents Inc. Aluminum alkyl with C5 cyclic and pendent olefin polymerization catalyst
WO2016195824A1 (en) 2015-05-29 2016-12-08 Exxonmobil Chemical Patents Inc. Polymerization process using bridged metallocene compounds supported on organoaluminum treated layered silicate supports
US10618988B2 (en) 2015-08-31 2020-04-14 Exxonmobil Chemical Patents Inc. Branched propylene polymers produced via use of vinyl transfer agents and processes for production thereof
WO2017039995A1 (en) 2015-08-31 2017-03-09 Exxonmobil Chemical Patents Inc. Aluminum alkyls with pendant olefins for polyolefin reactions
US10676547B2 (en) 2015-08-31 2020-06-09 Exxonmobil Chemical Patents Inc. Aluminum alkyls with pendant olefins on clays
US10059788B2 (en) 2016-04-29 2018-08-28 Exxonmobil Chemical Patents Inc. Organoaluminum activators on clays
US10562987B2 (en) 2016-06-30 2020-02-18 Exxonmobil Chemical Patents Inc. Polymers produced via use of quinolinyldiamido transition metal complexes and vinyl transfer agents
JP6902337B2 (ja) 2016-08-03 2021-07-14 住友化学株式会社 ヘテロファジックプロピレン重合材料の製造方法
US10626200B2 (en) 2017-02-28 2020-04-21 Exxonmobil Chemical Patents Inc. Branched EPDM polymers produced via use of vinyl transfer agents and processes for production thereof
WO2018160278A1 (en) 2017-03-01 2018-09-07 Exxonmobil Chemical Patents Inc. Branched ethylene copolymers produced via use of vinyl transfer agents and processes for production thereof
WO2022268957A1 (en) 2021-06-24 2022-12-29 Borealis Ag Method for determining compressive character of olefin polymerisation catalysts

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TW218884B (de) * 1991-05-01 1994-01-11 Mitsubishi Kakoki Kk
US5399636A (en) * 1993-06-11 1995-03-21 Phillips Petroleum Company Metallocenes and processes therefor and therewith
EP0658576B1 (de) * 1993-12-17 1998-07-29 Tosoh Corporation Olefinpolymerisationkatalysator und Verfahren zur Olefinpolymerisation
DE69525679T2 (de) * 1994-05-18 2002-11-07 Mitsubishi Chem Corp Katalysator zur Polymerisation eines Olefins und Verfahren zum Polymerisieren des Olefins

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10314369A1 (de) * 2003-03-28 2004-10-14 Otto-Von-Guericke-Universität Magdeburg Polymerisationskatalysatoren auf Porenbetonbasis, Verfahren und ihre Herstellung und ihre Verwendung
DE10314369B4 (de) * 2003-03-28 2005-08-25 Otto-Von-Guericke-Universität Magdeburg Polymerisationskatalysatoren auf Porenbetonbasis, Verfahren zu ihrer Herstellung und ihre Verwendung

Also Published As

Publication number Publication date
US6048817A (en) 2000-04-11
CN1197802A (zh) 1998-11-04
DE69801299D1 (de) 2001-09-13
CN1100798C (zh) 2003-02-05
EP0874006A1 (de) 1998-10-28
US6444763B1 (en) 2002-09-03
EP0874006B1 (de) 2001-08-08

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