TW593415B - Process and apparatus for producing polyesters, copolyesters and polycarbonates - Google Patents
Process and apparatus for producing polyesters, copolyesters and polycarbonates Download PDFInfo
- Publication number
- TW593415B TW593415B TW092108927A TW92108927A TW593415B TW 593415 B TW593415 B TW 593415B TW 092108927 A TW092108927 A TW 092108927A TW 92108927 A TW92108927 A TW 92108927A TW 593415 B TW593415 B TW 593415B
- Authority
- TW
- Taiwan
- Prior art keywords
- stage
- polycondensation
- reactor
- reaction
- patent application
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920000728 polyester Polymers 0.000 title claims abstract description 8
- 229920000515 polycarbonate Polymers 0.000 title claims description 4
- 239000004417 polycarbonate Substances 0.000 title claims description 4
- 229920001634 Copolyester Polymers 0.000 title claims description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 48
- 238000005886 esterification reaction Methods 0.000 claims abstract description 26
- 230000032050 esterification Effects 0.000 claims abstract description 22
- 150000002009 diols Chemical class 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims description 13
- -1 diaryl carbonate Chemical compound 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000005809 transesterification reaction Methods 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000052 vinegar Substances 0.000 claims description 3
- 235000021419 vinegar Nutrition 0.000 claims description 3
- 238000010924 continuous production Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 241000252185 Cobitidae Species 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 238000005453 pelletization Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 150000001991 dicarboxylic acids Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 33
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/20—Stationary reactors having moving elements inside in the form of helices, e.g. screw reactors
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1856—Stationary reactors having moving elements inside placed in parallel
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/785—Preparation processes characterised by the apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/205—General preparatory processes characterised by the apparatus used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/18—Details relating to the spatial orientation of the reactor
- B01J2219/182—Details relating to the spatial orientation of the reactor horizontal
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10219671A DE10219671A1 (de) | 2002-05-02 | 2002-05-02 | Verfahren und Vorrichtung zur Herstellung von Polyestern, Copolyestern und Polycarbonaten |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW200404082A TW200404082A (en) | 2004-03-16 |
| TW593415B true TW593415B (en) | 2004-06-21 |
Family
ID=29265005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW092108927A TW593415B (en) | 2002-05-02 | 2003-04-17 | Process and apparatus for producing polyesters, copolyesters and polycarbonates |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US7084234B2 (enExample) |
| EP (1) | EP1444286B1 (enExample) |
| JP (1) | JP2005524731A (enExample) |
| KR (1) | KR100925931B1 (enExample) |
| CN (1) | CN100393772C (enExample) |
| AT (1) | ATE328024T1 (enExample) |
| AU (1) | AU2003226771A1 (enExample) |
| DE (2) | DE10219671A1 (enExample) |
| EA (1) | EA008507B1 (enExample) |
| ES (1) | ES2263994T3 (enExample) |
| MY (1) | MY135132A (enExample) |
| TW (1) | TW593415B (enExample) |
| WO (1) | WO2003093345A1 (enExample) |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6906164B2 (en) | 2000-12-07 | 2005-06-14 | Eastman Chemical Company | Polyester process using a pipe reactor |
| KR100507698B1 (ko) * | 2002-05-31 | 2005-08-11 | 주식회사 효성 | 뱃치식 폴리에스터 중합장치 |
| DE10320074A1 (de) * | 2003-05-05 | 2004-12-02 | Bühler AG | Reaktor und Verfahren zur Behandlung von Schüttgütern |
| DE10336164B4 (de) * | 2003-08-07 | 2005-08-25 | Zimmer Ag | Verfahren und Vorrichtung zur kontinuierlichen Herstellung von Polymeren durch Schmelzkondensation |
| DE10337780B4 (de) * | 2003-08-14 | 2005-12-08 | Zimmer Ag | Verfahren zur kontinuierlichen Herstellung von Polymeren durch Schmelzkondensation |
| DE102005034455B3 (de) * | 2005-07-23 | 2006-11-02 | Zimmer Ag | Vorrichtung zur Schmelzepolykondensation mit einem Reaktorkäfig |
| JP5044555B2 (ja) * | 2005-08-24 | 2012-10-10 | ビーエーエスエフ ソシエタス・ヨーロピア | 吸水性ポリマー粒子の製造方法 |
| ES2290926T3 (es) * | 2006-01-24 | 2008-02-16 | Lurgi Zimmer Gmbh | Procedimiento para la esterificacion de acido tereftalico con butanodiol, procedimiento para la preparacion de poli(tereftalato de butileno)y dispositivo para ello. |
| US7943094B2 (en) * | 2006-12-07 | 2011-05-17 | Grupo Petrotemex, S.A. De C.V. | Polyester production system employing horizontally elongated esterification vessel |
| US7649109B2 (en) | 2006-12-07 | 2010-01-19 | Eastman Chemical Company | Polyester production system employing recirculation of hot alcohol to esterification zone |
| US20080139780A1 (en) * | 2006-12-07 | 2008-06-12 | Debruin Bruce Roger | Polyester production system employing short residence time esterification |
| US7863477B2 (en) | 2007-03-08 | 2011-01-04 | Eastman Chemical Company | Polyester production system employing hot paste to esterification zone |
| US7892498B2 (en) | 2007-03-08 | 2011-02-22 | Eastman Chemical Company | Polyester production system employing an unagitated esterification reactor |
| US7872090B2 (en) | 2007-07-12 | 2011-01-18 | Eastman Chemical Company | Reactor system with optimized heating and phase separation |
| US7842777B2 (en) | 2007-07-12 | 2010-11-30 | Eastman Chemical Company | Sloped tubular reactor with divided flow |
| US7829653B2 (en) | 2007-07-12 | 2010-11-09 | Eastman Chemical Company | Horizontal trayed reactor |
| US7858730B2 (en) | 2007-07-12 | 2010-12-28 | Eastman Chemical Company | Multi-level tubular reactor with dual headers |
| US7872089B2 (en) | 2007-07-12 | 2011-01-18 | Eastman Chemical Company | Multi-level tubular reactor with internal tray |
| US7868130B2 (en) | 2007-07-12 | 2011-01-11 | Eastman Chemical Company | Multi-level tubular reactor with vertically spaced segments |
| US7868129B2 (en) | 2007-07-12 | 2011-01-11 | Eastman Chemical Company | Sloped tubular reactor with spaced sequential trays |
| US7847053B2 (en) | 2007-07-12 | 2010-12-07 | Eastman Chemical Company | Multi-level tubular reactor with oppositely extending segments |
| DE102007050929B4 (de) * | 2007-10-23 | 2012-10-25 | Lurgi Zimmer Gmbh | Verfahren und Vorrichtung zur Erzeugung von Vakuum bei der Herstellung von Polyestern und Copolyestern |
| US7834109B2 (en) * | 2007-12-07 | 2010-11-16 | Eastman Chemical Company | System for producing low impurity polyester |
| DE102008044440B4 (de) * | 2008-08-18 | 2011-03-03 | Lurgi Zimmer Gmbh | Verfahren und Vorrichtung zur Rückgewinnung von Ethylenglykol bei der Polyethylenterephthalatherstellung |
| DE102011082769A1 (de) * | 2011-09-15 | 2013-03-21 | Lindauer Dornier Gesellschaft Mit Beschränkter Haftung | Verfahren und Vorrichtung zum Entgasen einer PET - Kunststoffschmelze in einer Extrusionsanlage |
| DE102012105296A1 (de) | 2012-06-19 | 2013-12-19 | Epc Engineering Consulting Gmbh | Verfahren und Anlage zur Herstellung von Polycarbonat |
| DK3467005T3 (da) * | 2016-05-30 | 2020-09-28 | Sa Minera Catalano Aragonesa | Fremgangsmåde til opnåelse af bionedbrydeligt polyesteretheramid |
| EP3500616B1 (en) | 2016-08-18 | 2021-03-24 | Eastman Chemical Company | Polyester compositions which comprise tetramethylcyclobutandiol and ethylene glycol, with improved catalyst system |
| CN109563247B (zh) | 2016-08-18 | 2021-10-08 | 伊士曼化工公司 | 使用改进的催化剂体系的包含四甲基环丁二醇和乙二醇的聚酯组合物 |
| WO2018035341A1 (en) | 2016-08-18 | 2018-02-22 | Eastman Chemical Company | Polyester compositions which comprise tetramethylcyclobutanediol and ethylene glycol for calendering |
| CN108948340B (zh) * | 2018-06-05 | 2021-03-09 | 金聚合科技(宁波)有限公司 | 一种制备芳香族聚碳酸酯的装置及方法 |
| WO2025109040A1 (en) | 2023-11-22 | 2025-05-30 | Sabic Global Technologies B.V. | Process for producing polycarbonate |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL128231C (enExample) * | 1963-12-26 | |||
| FR1418672A (fr) * | 1963-12-26 | 1965-11-19 | Toyo Rayon Co Ltd | Appareil de production en continu de produits de réaction de polycondensation |
| JPS5236554B2 (enExample) | 1973-06-27 | 1977-09-16 | ||
| US4831108A (en) * | 1983-02-16 | 1989-05-16 | Amoco Corporation | Polycondensation process with mean dispersion residence time |
| JPS61207429A (ja) * | 1985-03-08 | 1986-09-13 | Toyobo Co Ltd | ポリエステルの連続重縮合方法 |
| SG78245A1 (en) * | 1993-07-23 | 2001-02-20 | Ashi Kasei Kogyo Kabushiki Kai | Method for producing an aromatic polycarbonate |
| DE19753378A1 (de) * | 1997-12-02 | 1999-06-10 | Lurgi Zimmer Ag | Verfahren zur Herstellung von Polyestern mit Mischkatalysatoren |
| JP4144967B2 (ja) * | 1999-04-22 | 2008-09-03 | 帝人ファイバー株式会社 | 横型反応装置 |
| JP3428978B2 (ja) * | 1999-06-12 | 2003-07-22 | エルジー・ケミカル・カンパニー・リミテッド | 芳香族ポリカーボネートの製造方法及びその装置 |
| DE10001477B4 (de) * | 2000-01-15 | 2005-04-28 | Zimmer Ag | Diskontinuierliches Polykondensationsverfahren und Rührscheibenreaktor hierfür |
| US6359106B1 (en) * | 2000-03-09 | 2002-03-19 | Hitachi, Ltd. | Production process and production apparatus for polybutylene terephthalate |
| PT1453883E (pt) * | 2000-12-07 | 2013-03-04 | Grupo Petrotemex Sa De Cv | Processo de preparação de poliéster de baixo custo utilizando um reactor tubular |
-
2002
- 2002-05-02 DE DE10219671A patent/DE10219671A1/de not_active Withdrawn
- 2002-07-30 CN CNB021584451A patent/CN100393772C/zh not_active Expired - Lifetime
-
2003
- 2003-04-02 KR KR1020047017444A patent/KR100925931B1/ko not_active Expired - Fee Related
- 2003-04-02 AT AT03747404T patent/ATE328024T1/de not_active IP Right Cessation
- 2003-04-02 JP JP2004501484A patent/JP2005524731A/ja active Pending
- 2003-04-02 EA EA200401439A patent/EA008507B1/ru not_active IP Right Cessation
- 2003-04-02 WO PCT/EP2003/003412 patent/WO2003093345A1/de not_active Ceased
- 2003-04-02 ES ES03747404T patent/ES2263994T3/es not_active Expired - Lifetime
- 2003-04-02 EP EP03747404A patent/EP1444286B1/de not_active Expired - Lifetime
- 2003-04-02 DE DE50303563T patent/DE50303563D1/de not_active Expired - Lifetime
- 2003-04-02 AU AU2003226771A patent/AU2003226771A1/en not_active Abandoned
- 2003-04-02 US US10/513,227 patent/US7084234B2/en not_active Expired - Lifetime
- 2003-04-17 TW TW092108927A patent/TW593415B/zh not_active IP Right Cessation
- 2003-04-30 MY MYPI20031638A patent/MY135132A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR20050006212A (ko) | 2005-01-15 |
| CN100393772C (zh) | 2008-06-11 |
| TW200404082A (en) | 2004-03-16 |
| ES2263994T3 (es) | 2006-12-16 |
| DE10219671A1 (de) | 2003-11-20 |
| US20050222371A1 (en) | 2005-10-06 |
| DE50303563D1 (de) | 2006-07-06 |
| WO2003093345A1 (de) | 2003-11-13 |
| CN1454913A (zh) | 2003-11-12 |
| EP1444286B1 (de) | 2006-05-31 |
| MY135132A (en) | 2008-02-29 |
| JP2005524731A (ja) | 2005-08-18 |
| EP1444286A1 (de) | 2004-08-11 |
| EA200401439A1 (ru) | 2005-06-30 |
| ATE328024T1 (de) | 2006-06-15 |
| US7084234B2 (en) | 2006-08-01 |
| EA008507B1 (ru) | 2007-06-29 |
| AU2003226771A1 (en) | 2003-11-17 |
| KR100925931B1 (ko) | 2009-11-09 |
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