ATE291039T1 - Olefinpolymerisation - Google Patents

Olefinpolymerisation

Info

Publication number
ATE291039T1
ATE291039T1 AT99936001T AT99936001T ATE291039T1 AT E291039 T1 ATE291039 T1 AT E291039T1 AT 99936001 T AT99936001 T AT 99936001T AT 99936001 T AT99936001 T AT 99936001T AT E291039 T1 ATE291039 T1 AT E291039T1
Authority
AT
Austria
Prior art keywords
olefin polymerization
diimine
complexed
elastomers
polymerized
Prior art date
Application number
AT99936001T
Other languages
English (en)
Inventor
Lynda Kaye Johnson
Lissa Taka Jennings Nelson
Original Assignee
Du Pont
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
Application filed by Du Pont filed Critical Du Pont
Application granted granted Critical
Publication of ATE291039T1 publication Critical patent/ATE291039T1/de

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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
    • 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
    • C08F4/60003—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 the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
    • C08F4/60006—Bidentate ligand
    • C08F4/60041—Monoanionic ligand
    • C08F4/60044—NN
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/04—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers
    • C07C257/06—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers having carbon atoms of imino-carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms, or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/06—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D243/00—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms
    • C07D243/06—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4
    • C07D243/08—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4 not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/005—Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5027—Polyphosphines
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—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
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • 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
    • C08F210/02—Ethene

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
AT99936001T 1998-07-29 1999-07-29 Olefinpolymerisation ATE291039T1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US9450298P 1998-07-29 1998-07-29
PCT/US1999/017332 WO2000006620A2 (en) 1998-07-29 1999-07-29 Polymerization of olefins

Publications (1)

Publication Number Publication Date
ATE291039T1 true ATE291039T1 (de) 2005-04-15

Family

ID=22245541

Family Applications (1)

Application Number Title Priority Date Filing Date
AT99936001T ATE291039T1 (de) 1998-07-29 1999-07-29 Olefinpolymerisation

Country Status (13)

Country Link
US (2) US6403738B1 (de)
EP (1) EP1115758B1 (de)
JP (1) JP2002521538A (de)
KR (1) KR20010072085A (de)
CN (1) CN1195783C (de)
AT (1) ATE291039T1 (de)
AU (1) AU761155B2 (de)
BR (1) BR9912690A (de)
CA (1) CA2338686A1 (de)
DE (1) DE69924267T2 (de)
EA (1) EA200100189A1 (de)
NO (1) NO20010459L (de)
WO (1) WO2000006620A2 (de)

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6660677B1 (en) * 1997-03-10 2003-12-09 Eastman Chemical Company Supported group 8-10 transition metal olefin polymerization catalysts
US6822062B2 (en) 1997-03-10 2004-11-23 Eastman Chemical Company Supported group 8-10 transition metal olefin polymerization catalysts
US6245871B1 (en) * 1997-04-18 2001-06-12 Eastman Chemical Company Group 8-10 transition metal olefin polymerization catalysts
AU2760599A (en) * 1998-02-04 1999-08-23 Friedman, Robert F. Method and apparatus for combining transponders on multiple satellites into virtual channels
US6545108B1 (en) * 1999-02-22 2003-04-08 Eastman Chemical Company Catalysts containing N-pyrrolyl substituted nitrogen donors
WO2000050470A2 (en) * 1999-02-22 2000-08-31 Eastman Chemical Company Catalysts containing n-pyrrolyl substituted nitrogen donors
US6620896B1 (en) * 1999-02-23 2003-09-16 Eastman Chemical Company Mixed olefin polymerization catalysts, processes employing such catalysts, and polymers obtained therefrom
US6380327B1 (en) 1999-11-12 2002-04-30 E. I. Du Pont De Nemours And Company Chain transfer agents for olefin polymerization
US6579823B2 (en) * 2000-02-18 2003-06-17 Eastman Chemical Company Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors
US6521724B2 (en) 2000-03-10 2003-02-18 E. I. Du Pont De Nemours And Company Polymerization process
DE60005640T2 (de) * 2000-03-13 2004-07-29 Repsol Quimica S.A. Zweizähnige Nickel- und Palladium-komplexe und Polymerisationskatalysatoren
US6737130B2 (en) 2001-11-06 2004-05-18 Cryovac, Inc. Hermetically heat-sealable, pressure-reclosable packaging article containing substantially spherical homogeneous polyolefin
US6761965B2 (en) 2001-11-06 2004-07-13 Cryovac, Inc. Irradiated multilayer film having seal layer containing hyperbranched polymer
US6733851B2 (en) 2001-11-06 2004-05-11 Cryovac, Inc. Packaging article having heat seal layer containing blend of hyperbranched and semicrystalline olefin polymers
US6930070B2 (en) * 2002-01-28 2005-08-16 Univation Technologies, Llc Heterocyclic nitrogen-containing activators and catalyst systems for olefin polymerization
US7741417B2 (en) * 2004-01-07 2010-06-22 Exxonmobil Chemical Patents Inc. Preparation of polymerization catalyst activators utilizing indole-modified silica supports
WO2005087824A1 (en) * 2004-03-02 2005-09-22 Bridgestone Corporation Bulk polymerization process
US7560523B2 (en) * 2005-08-25 2009-07-14 Cornell Research Foundation, Inc. Production of isotactic and regiorandom polypropylene based polymer and block copolymers
CN100465195C (zh) * 2006-04-29 2009-03-04 中国科学院长春应用化学研究所 一种β-羟基丙烯亚胺钒烯烃聚合催化剂及制备方法和应用
US8022005B2 (en) * 2007-11-08 2011-09-20 Exxonmobil Chemical Patents Inc. Halogen substituted heterocyclic heteroatom containing ligands-alumoxane activation of metallocenes
CN101274939B (zh) * 2008-05-16 2012-05-09 华东理工大学 新型β-二亚胺类锆化合物及其制备方法和应用
JP6175052B2 (ja) 2011-05-16 2017-08-02 上海 インスティテュート オブ オーガニック ケミストリー、チャイニーズ アカデミー オブ サイエンシーズShanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences オレフィンから高分岐アルカンを製造する触媒系
NO335188B1 (no) 2012-10-22 2014-10-20 Scandinavian Business Seating AS Justerbar armlenesammenstilling
KR101621251B1 (ko) * 2014-04-24 2016-05-16 서강대학교산학협력단 신규한 비스아미딘 구조의 전이금속 착물 및 이를 이용한 올레핀 중합 방법
CN107629160B (zh) * 2016-07-19 2020-05-08 中国石油天然气股份有限公司 一种乙烯与甲基丙烯酸甲酯共聚的方法
CN107698699B (zh) * 2017-09-27 2021-01-29 常州大学 用于催化乙烯和2-己烯聚合的含有对位二苯甲基取代的α-二亚胺镍(Ⅱ)配合物
WO2021083350A1 (zh) 2019-10-31 2021-05-06 中国石油化工股份有限公司 二亚胺金属配合物及其制备方法和应用
US12404292B2 (en) 2019-10-31 2025-09-02 China Petroleum & Chemical Corporation Amino-imine metal complex and preparation method therefor and application thereof
KR102953256B1 (ko) 2019-10-31 2026-04-15 차이나 페트로리움 앤드 케미컬 코포레이션 올레핀-극성 단량체 공중합체의 제조 방법
EP4107195B1 (de) * 2020-02-17 2024-11-20 Universita' Degli Studi Di Trieste Katalysatoren und verfahren zur copolymerisation von olefinen und polaren vinylmonomeren und zur homopolymerisation von olefinen
CN111362838B (zh) * 2020-04-14 2021-05-07 中国科学技术大学 含脲基团二亚胺钯催化剂及其配体以及在烯烃聚合中的应用

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
US5880241A (en) 1995-01-24 1999-03-09 E. I. Du Pont De Nemours And Company Olefin polymers
JP3847783B2 (ja) 1995-01-24 2006-11-22 イー・アイ・デュポン・ドゥ・ヌムール・アンド・カンパニー オレフィンの重合方法
US5714556A (en) 1995-06-30 1998-02-03 E. I. Dupont De Nemours And Company Olefin polymerization process
CA2259582A1 (en) * 1996-07-23 1998-01-29 Stephan James Mclain Polymerization processes for olefins
JP2001512522A (ja) * 1997-02-25 2001-08-21 イーストマン ケミカル カンパニー 官能化オレフィンモノマーを含有するポリマー
JP2002514252A (ja) * 1997-03-10 2002-05-14 イーストマン ケミカル カンパニー 第8〜10族遷移金属を含むオレフィン重合触媒、二座配位子、このような触媒の使用方法及びそれから得られるポリマー
US6103658A (en) * 1997-03-10 2000-08-15 Eastman Chemical Company Olefin polymerization catalysts containing group 8-10 transition metals, processes employing such catalysts and polymers obtained therefrom
CA2276254A1 (en) 1997-03-13 1998-09-17 James Allen Ponasik Jr. Catalyst compositions for the polymerization of olefins
EP0975682B1 (de) 1997-04-18 2004-05-19 Eastman Chemical Company Gruppe 8-10 übergangsmetallkatalysator für die polymerisation von olefinen

Also Published As

Publication number Publication date
DE69924267D1 (de) 2005-04-21
NO20010459L (no) 2001-03-22
BR9912690A (pt) 2001-05-08
WO2000006620A2 (en) 2000-02-10
AU761155B2 (en) 2003-05-29
AU5136099A (en) 2000-02-21
KR20010072085A (ko) 2001-07-31
EP1115758A2 (de) 2001-07-18
US20020156212A1 (en) 2002-10-24
US6403738B1 (en) 2002-06-11
DE69924267T2 (de) 2006-02-09
CN1195783C (zh) 2005-04-06
WO2000006620A3 (en) 2000-06-22
NO20010459D0 (no) 2001-01-26
US6770771B2 (en) 2004-08-03
EA200100189A1 (ru) 2001-08-27
CN1320130A (zh) 2001-10-31
JP2002521538A (ja) 2002-07-16
CA2338686A1 (en) 2000-02-10
EP1115758B1 (de) 2005-03-16

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