AR041876A1 - Sintesis de componentes catalizadores de la polimerizacion - Google Patents
Sintesis de componentes catalizadores de la polimerizacionInfo
- Publication number
- AR041876A1 AR041876A1 ARP030103975A ARP030103975A AR041876A1 AR 041876 A1 AR041876 A1 AR 041876A1 AR P030103975 A ARP030103975 A AR P030103975A AR P030103975 A ARP030103975 A AR P030103975A AR 041876 A1 AR041876 A1 AR 041876A1
- Authority
- AR
- Argentina
- Prior art keywords
- less
- equal
- particular embodiment
- fluorinated
- metallocene
- Prior art date
Links
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000006116 polymerization reaction Methods 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract 2
- 229910052731 fluorine Inorganic materials 0.000 abstract 2
- 239000011737 fluorine Substances 0.000 abstract 2
- 239000012968 metallocene catalyst Substances 0.000 abstract 2
- 238000000034 method Methods 0.000 abstract 2
- OKICHZSTRJQITD-UHFFFAOYSA-N 5-methylcyclopenta-1,3-diene zirconium(2+) Chemical compound [Zr++].C[c-]1cccc1.C[c-]1cccc1 OKICHZSTRJQITD-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- ZMMRKRFMSDTOLV-UHFFFAOYSA-N cyclopenta-1,3-diene zirconium Chemical group [Zr].C1C=CC=C1.C1C=CC=C1 ZMMRKRFMSDTOLV-UHFFFAOYSA-N 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- 238000004334 fluoridation Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
Classifications
-
- 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
-
- 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
- C07F17/00—Metallocenes
-
- 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
- C08F4/42—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
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/26—Fluorinating
-
- 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
- C08F2420/00—Metallocene catalysts
- C08F2420/05—Cp or analog where at least one of the carbon atoms of the coordinating ring is replaced by a heteroatom
-
- 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
- C08F4/65925—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 non-bridged
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
La presente provee un método para sintetizar componentes catalizadores de metaloceno fluorurados que comprende poner en contacto al menos un agente de fluoruración que comprende flúor con uno o más componentes catalizadores de metaloceno alquilados que comprenden uno o más grupo salientes no halogenados para producir un componente catalizador fluorurado; donde entre menos de 3 equivalentes de flúor entran en contacto por cada equivalente de grupo saliente. El método de la presente es ejemplificado mediante la siguiente reacción de fórmula (1), la cual se produce en un diluyente no coordinador tal como pentano; donde uno o ambos de los anillos de "Cp" pueden estar sustituidos con un grupo R según lo descrito en la presente, y pueden estar puenteados. La reacción puede llevarse a cabo a cualquier temperatura deseable, deseablemente entre 10° C y 35° C. el producto de reacción del BF3 y dimetilzirconoceno es el zirconoceno fluorurado. La relación molar del agente de fluorutación BF3 y el metaloceno de partida es inferior a 2:1 (agente de fluoruración: metaloceno) en una realización, e inferior a o igual a 1,6:1 en una realización particular, e inferior o igual a 1,5:1 en una realización más particular, e inferior o igual a 1,2:1 en aún una realización más particular.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/290,122 US6869903B2 (en) | 2002-11-07 | 2002-11-07 | Synthesis of polymerization catalyst components |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AR041876A1 true AR041876A1 (es) | 2005-06-01 |
Family
ID=32228990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ARP030103975A AR041876A1 (es) | 2002-11-07 | 2003-10-30 | Sintesis de componentes catalizadores de la polimerizacion |
Country Status (16)
| Country | Link |
|---|---|
| US (2) | US6869903B2 (es) |
| EP (1) | EP1560857A4 (es) |
| JP (1) | JP2006505670A (es) |
| KR (1) | KR100684253B1 (es) |
| CN (1) | CN100358922C (es) |
| AR (1) | AR041876A1 (es) |
| AU (1) | AU2003282528A1 (es) |
| BR (1) | BR0316089A (es) |
| CA (1) | CA2502687A1 (es) |
| MX (1) | MXPA05004868A (es) |
| MY (1) | MY142486A (es) |
| PL (1) | PL376328A1 (es) |
| RU (1) | RU2327704C2 (es) |
| TW (1) | TW200415160A (es) |
| WO (1) | WO2004044010A2 (es) |
| ZA (1) | ZA200502719B (es) |
Families Citing this family (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7838708B2 (en) | 2001-06-20 | 2010-11-23 | Grt, Inc. | Hydrocarbon conversion process improvements |
| US6900154B2 (en) * | 2002-11-26 | 2005-05-31 | Univation Technologies, Llc | Methods of forming a supported activated catalyst composition |
| US7247158B2 (en) * | 2003-02-04 | 2007-07-24 | Wright Medical Technology, Inc. | Acetabular impactor |
| ATE471332T1 (de) * | 2003-05-08 | 2010-07-15 | Basell Polyolefine Gmbh | Verfahren zur herstellung von halogenidmetallocenverbindungen |
| US20050171393A1 (en) | 2003-07-15 | 2005-08-04 | Lorkovic Ivan M. | Hydrocarbon synthesis |
| 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 |
| US20060100469A1 (en) | 2004-04-16 | 2006-05-11 | Waycuilis John J | Process for converting gaseous alkanes to olefins and liquid hydrocarbons |
| US8642822B2 (en) | 2004-04-16 | 2014-02-04 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
| US7674941B2 (en) | 2004-04-16 | 2010-03-09 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| US7244867B2 (en) | 2004-04-16 | 2007-07-17 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US20080275284A1 (en) | 2004-04-16 | 2008-11-06 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US8173851B2 (en) | 2004-04-16 | 2012-05-08 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| SG187456A1 (en) | 2006-02-03 | 2013-02-28 | Grt Inc | Separation of light gases from halogens |
| AP2673A (en) | 2006-02-03 | 2013-05-23 | Grt Inc | Continuous process for converting natural gas to liquid hydrocarbons |
| MX2009012581A (es) | 2007-05-24 | 2010-03-15 | Grt Inc | Reactor de zonas que incorpora captura y liberacion de haluro de hidrogeno reversible. |
| US8022005B2 (en) | 2007-11-08 | 2011-09-20 | Exxonmobil Chemical Patents Inc. | Halogen substituted heterocyclic heteroatom containing ligands-alumoxane activation of metallocenes |
| US8282810B2 (en) | 2008-06-13 | 2012-10-09 | Marathon Gtf Technology, Ltd. | Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery |
| US8273929B2 (en) | 2008-07-18 | 2012-09-25 | Grt, Inc. | Continuous process for converting natural gas to liquid hydrocarbons |
| US8367884B2 (en) | 2010-03-02 | 2013-02-05 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8198495B2 (en) | 2010-03-02 | 2012-06-12 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8815050B2 (en) | 2011-03-22 | 2014-08-26 | Marathon Gtf Technology, Ltd. | Processes and systems for drying liquid bromine |
| US8436220B2 (en) | 2011-06-10 | 2013-05-07 | Marathon Gtf Technology, Ltd. | Processes and systems for demethanization of brominated hydrocarbons |
| US8829256B2 (en) | 2011-06-30 | 2014-09-09 | Gtc Technology Us, Llc | Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons |
| US8802908B2 (en) | 2011-10-21 | 2014-08-12 | Marathon Gtf Technology, Ltd. | Processes and systems for separate, parallel methane and higher alkanes' bromination |
| US9193641B2 (en) | 2011-12-16 | 2015-11-24 | Gtc Technology Us, Llc | Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems |
| RU2734065C9 (ru) * | 2014-02-11 | 2020-11-26 | ЮНИВЕЙШН ТЕКНОЛОДЖИЗ, ЭлЭлСи | Получение полиолефиновых продуктов |
| CN104190404B (zh) * | 2014-09-17 | 2016-05-18 | 桂林理工大学 | 可见光响应的光催化剂SmNbMo2O10及其制备方法 |
| US10266618B2 (en) * | 2014-11-24 | 2019-04-23 | Univation Technologies, Llc | Chromium-based catalyst compositions for olefin polymerization |
| US10351647B2 (en) | 2015-05-29 | 2019-07-16 | Exxonmobil Chemical Patents Inc. | Polymerization process using bridged metallocene compounds supported on organoaluminum treated layered silicate supports |
| ES2839923T3 (es) * | 2016-09-30 | 2021-07-06 | Univation Tech Llc | Catalizadores de polimerización con encadenamiento de etileno mejorado |
| WO2018151790A1 (en) | 2017-02-20 | 2018-08-23 | Exxonmobil Chemical Patents Inc. | Hafnocene catalyst compounds and process for use thereof |
| US10479846B2 (en) | 2017-02-20 | 2019-11-19 | Exxonmobil Chemical Patents Inc. | Hafnocene catalyst compounds and process for use thereof |
| EP3583137B1 (en) * | 2017-02-20 | 2024-05-29 | ExxonMobil Chemical Patents Inc. | Hafnocene catalyst compounds and process for use thereof |
| WO2021194831A1 (en) * | 2020-03-25 | 2021-09-30 | Exxonmobil Chemical Patents Inc. | Alkylation of transition metal coordination catalyst complexes |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3678024D1 (de) | 1985-03-26 | 1991-04-18 | Mitsui Petrochemical Ind | Fluessiges statisches ethylencopolymer, verfahren zur herstellung und anwendung desselben. |
| ES2156153T3 (es) | 1993-06-15 | 2001-06-16 | Idemitsu Kosan Co | Procedimiento de produccion de polimero olefinico, y catalizador para la polimerizacion de una olefina. |
| DE4332009A1 (de) | 1993-09-21 | 1995-03-30 | Hoechst Ag | Verfahren zur Herstellung von Organometallfluoriden |
| EP0857179A1 (de) | 1995-08-18 | 1998-08-12 | Basell Polyolefine GmbH | Katalysatorkomponente und katalysatorsystem mit hoher polymerisationsaktivität zur herstellung von polymeren |
| US6632901B2 (en) | 1998-08-21 | 2003-10-14 | Univation Technologies, Llc | Polymerization process using an improved bulky ligand metallocene-type catalyst system |
| DE10053486A1 (de) * | 2000-10-27 | 2002-05-08 | Bayer Ag | Zusammensetzung auf Basis von Monofluormetallkomplexen |
-
2002
- 2002-11-07 US US10/290,122 patent/US6869903B2/en not_active Expired - Fee Related
-
2003
- 2003-10-08 RU RU2005117610/04A patent/RU2327704C2/ru not_active IP Right Cessation
- 2003-10-08 EP EP03774719A patent/EP1560857A4/en not_active Ceased
- 2003-10-08 KR KR1020057008112A patent/KR100684253B1/ko not_active Expired - Fee Related
- 2003-10-08 JP JP2004551507A patent/JP2006505670A/ja active Pending
- 2003-10-08 AU AU2003282528A patent/AU2003282528A1/en not_active Abandoned
- 2003-10-08 WO PCT/US2003/032016 patent/WO2004044010A2/en not_active Ceased
- 2003-10-08 CA CA002502687A patent/CA2502687A1/en not_active Abandoned
- 2003-10-08 CN CNB2003801023871A patent/CN100358922C/zh not_active Expired - Fee Related
- 2003-10-08 MX MXPA05004868A patent/MXPA05004868A/es not_active Application Discontinuation
- 2003-10-08 PL PL03376328A patent/PL376328A1/xx not_active Application Discontinuation
- 2003-10-08 BR BR0316089-0A patent/BR0316089A/pt not_active IP Right Cessation
- 2003-10-29 TW TW092130101A patent/TW200415160A/zh unknown
- 2003-10-30 AR ARP030103975A patent/AR041876A1/es not_active Application Discontinuation
- 2003-11-05 MY MYPI20034220A patent/MY142486A/en unknown
-
2004
- 2004-06-23 US US10/875,137 patent/US6855784B2/en not_active Expired - Fee Related
-
2005
- 2005-04-04 ZA ZA200502719A patent/ZA200502719B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| MY142486A (en) | 2010-11-30 |
| US6855784B2 (en) | 2005-02-15 |
| AU2003282528A1 (en) | 2004-06-03 |
| WO2004044010A3 (en) | 2004-07-29 |
| US20040236045A1 (en) | 2004-11-25 |
| ZA200502719B (en) | 2005-10-20 |
| KR20050084977A (ko) | 2005-08-29 |
| CA2502687A1 (en) | 2004-05-27 |
| EP1560857A2 (en) | 2005-08-10 |
| EP1560857A4 (en) | 2006-04-19 |
| TW200415160A (en) | 2004-08-16 |
| CN100358922C (zh) | 2008-01-02 |
| US6869903B2 (en) | 2005-03-22 |
| RU2327704C2 (ru) | 2008-06-27 |
| JP2006505670A (ja) | 2006-02-16 |
| PL376328A1 (en) | 2005-12-27 |
| US20040092387A1 (en) | 2004-05-13 |
| KR100684253B1 (ko) | 2007-02-22 |
| BR0316089A (pt) | 2005-09-27 |
| CN1708516A (zh) | 2005-12-14 |
| MXPA05004868A (es) | 2005-08-19 |
| RU2005117610A (ru) | 2006-01-20 |
| WO2004044010A2 (en) | 2004-05-27 |
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