RU2008114851A - Алюминийсодержащие полиэфирные полимеры, обладающие низкими скоростями образования ацетальдегида - Google Patents
Алюминийсодержащие полиэфирные полимеры, обладающие низкими скоростями образования ацетальдегида Download PDFInfo
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- 229920000728 polyester Polymers 0.000 title claims abstract 47
- 229920000642 polymer Polymers 0.000 title claims abstract 15
- 238000000034 method Methods 0.000 claims abstract 17
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract 12
- 239000000155 melt Substances 0.000 claims abstract 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract 9
- 150000001340 alkali metals Chemical group 0.000 claims abstract 5
- 150000001342 alkaline earth metals Chemical group 0.000 claims abstract 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000005520 cutting process Methods 0.000 claims abstract 4
- 238000010128 melt processing Methods 0.000 claims abstract 4
- 238000006068 polycondensation reaction Methods 0.000 claims abstract 4
- 238000007711 solidification Methods 0.000 claims abstract 4
- 230000008023 solidification Effects 0.000 claims abstract 4
- 238000004519 manufacturing process Methods 0.000 claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract 2
- 239000011574 phosphorus Substances 0.000 claims abstract 2
- -1 phosphorus compound Chemical class 0.000 claims abstract 2
- 239000002245 particle Substances 0.000 claims 17
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims 14
- 239000008187 granular material Substances 0.000 claims 5
- 125000004429 atom Chemical group 0.000 claims 3
- 239000002253 acid Substances 0.000 claims 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- 239000007787 solid Substances 0.000 claims 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 1
- 239000006096 absorbing agent Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000011437 continuous method Methods 0.000 claims 1
- 238000001746 injection moulding Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 150000003503 terephthalic acid derivatives Chemical class 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- 229920001225 polyester resin Polymers 0.000 abstract 1
- 239000004645 polyester resin Substances 0.000 abstract 1
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- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
- B29C61/06—Making preforms having internal stresses, e.g. plastic memory
- B29C61/0608—Making preforms having internal stresses, e.g. plastic memory characterised by the configuration or structure of the preforms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D23/00—Details of bottles or jars not otherwise provided for
- B65D23/08—Coverings or external coatings
- B65D23/0807—Coatings
- B65D23/0814—Coatings characterised by the composition of the material
- B65D23/0828—Coatings characterised by the composition of the material consisting mainly of paints or lacquers
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
1. Непрерывный способ получения полиэфирных полимеров, включающий добавление атомов фосфора в расплав полиэфира, причем указанный расплав полиэфира содержит a) атомы алюминия и b) атомы щелочноземельного металла или атомы щелочного металла, или остатки щелочных соединений, где указанные атомы фосфора добавляют к расплаву полиэфира, когда удовлетворяется одно или несколько из следующих условий, или после этого и до затвердевания расплава полиэфира: ! a) It.V. расплава полиэфира достигает значения по меньшей мере 0,50 дл/г, или ! b) вакуум, приложенный к расплаву полиэфира, если он имеется, хотя бы частично уменьшен, или ! c) если в реакции полимеризации в расплаве присутствует расплав полиэфира, добавление соединения фосфора в конечный реактор получения полиэфирного полимера или после конечного реактора и до режущего устройства, предназначенного для резки полиэфирного расплава, или ! d) если в реакции полимеризации в расплаве присутствует расплав полиэфира, по истечении по меньшей мере 85% времени, отведенного для поликонденсации расплава полиэфира, или ! e) значение It.V. расплава полиэфира находится в пределах +/- 0,15 дл/г от значения It.V., полученного при затвердевании; или ! f) в момент времени за 20 мин или менее до затвердевания расплава полиэфира. ! 2. Способ по п.1, где расплав полиэфирного полимера присутствует в способе полимеризации в расплаве для получения указанного полиэфирного полимера. ! 3. Способ по п.1, где расплав полиэфира присутствует в зоне обработки расплава для производства изделия. ! 4. Способ по п.1, где в число указанных зон обработки расплава входит цилиндр экструдера. ! 5. Способ по п.4, где в число указанных зон �
Claims (27)
1. Непрерывный способ получения полиэфирных полимеров, включающий добавление атомов фосфора в расплав полиэфира, причем указанный расплав полиэфира содержит a) атомы алюминия и b) атомы щелочноземельного металла или атомы щелочного металла, или остатки щелочных соединений, где указанные атомы фосфора добавляют к расплаву полиэфира, когда удовлетворяется одно или несколько из следующих условий, или после этого и до затвердевания расплава полиэфира:
a) It.V. расплава полиэфира достигает значения по меньшей мере 0,50 дл/г, или
b) вакуум, приложенный к расплаву полиэфира, если он имеется, хотя бы частично уменьшен, или
c) если в реакции полимеризации в расплаве присутствует расплав полиэфира, добавление соединения фосфора в конечный реактор получения полиэфирного полимера или после конечного реактора и до режущего устройства, предназначенного для резки полиэфирного расплава, или
d) если в реакции полимеризации в расплаве присутствует расплав полиэфира, по истечении по меньшей мере 85% времени, отведенного для поликонденсации расплава полиэфира, или
e) значение It.V. расплава полиэфира находится в пределах +/- 0,15 дл/г от значения It.V., полученного при затвердевании; или
f) в момент времени за 20 мин или менее до затвердевания расплава полиэфира.
2. Способ по п.1, где расплав полиэфирного полимера присутствует в способе полимеризации в расплаве для получения указанного полиэфирного полимера.
3. Способ по п.1, где расплав полиэфира присутствует в зоне обработки расплава для производства изделия.
4. Способ по п.1, где в число указанных зон обработки расплава входит цилиндр экструдера.
5. Способ по п.4, где в число указанных зон обработки расплава входит цилиндр агрегата для литья под давлением.
6. Способ по п.1, где атомы фосфора добавляют в месте, расположенном рядом с конечным реактором или в его конечной части, или после конечного реактора и до агрегата резки, предназначенного для разрезания расплава полиэфирного полимера на частицы.
7. Способ по п.1, где атомы фосфора добавляют в конечный реактор, предназначенный для поликонденсации расплава полиэфира, через вход в виде трубки, причем указанные атомы фосфора содержатся в части полиэфирного полимера, выходящей из конечного реактора и подаваемой обратно в конечный реактор.
8. Способ по п.1, где атомы фосфора добавляют в расплав полиэфира по истечении по меньшей мере 95% времени поликонденсации.
9. Способ по п.1, где способ включает непрерывную реакцию полимеризации в расплаве, имеющую производительность не менее 1 тонны/сутки при установившемся режиме работы.
10. Способ по п.1, где время реакции расплава полиэфира от значения It.V. 0,40 дл/г и до значения It.V. в диапазоне от по меньшей мере 0,68 дл/г составляет 150 мин или менее.
11. Способ по п.1, где It.V. расплава полиэфира при затвердевании составляет от 0,82 дл/г до 0,92 дл/г перед добавлением атомов фосфора.
12. Способ по п.1, где полиэфирный полимер включает:
(a) кислотный компонент, включающий по меньшей мере 80 мол.% остатков терефталевой кислоты или производных терефталевой кислоты, и
(b) гидроксильный компонент, включающий по меньшей мере 80 мол.% остатков этиленгликоля,
в расчете на 100 мол.% остатков кислотного компонента и 100 мол.% остатков гидроксильного компонента в полиэфирном полимере.
13. Готовые частицы полиэфирного полимера, имеющие среднее значение It.V., полученное при полимеризации в расплаве, по меньшей мере 0,74 дл/г и остаточное содержание ацетальдегида 5 ч./млн. или менее, где указанные частицы имеют степень кристалличности по меньшей мере 30% и содержат атомы алюминия в количестве по меньшей мере 10 ч./млн. в расчете на массу полиэфирного полимера.
14. Частицы по п.13, помещенные в отгрузочный контейнер.
15. Частицы по п.13, содержащие отличное от нуля количество атомов щелочноземельного металла или атомов щелочного металла, а также отличное от нуля количество атомов фосфора.
16. Частицы по п.15, где скорость образования ацетальдегида в указанных частицах составляет менее 15 ч./млн.
17. Частицы по п.15, где значение параметра яркости L* указанных частиц составляет по меньшей мере 60.
18. Частицы по п.13, где частицы не содержат органических поглотителей ацетальдегида.
19. Частицы по п.13, где частицы не полимеризованы в твердом состоянии.
20. Частицы по п.13, где из частиц отливают преформы бутылок.
21. Частицы по п.20, где из частиц отливают преформы при температуре в диапазоне от 280 до 290°C при времени пребывания в расплавленном состоянии, равном 2 мин или менее, где преформы имеют значение параметра яркости L* 65 или более.
22. Изделия, полученные путем подачи гранул в зону обработки расплава, плавления гранул с образованием расплава полиэфира и формования изделия из расплава полиэфира, где указанные гранулы имеют значение It.V. по меньшей мере 0,72 дл/г и не подвергались полимеризации в твердом состоянии, причем указанные гранулы содержат полиэфирные полимеры и:
a) атомы алюминия; и
b) атомы щелочноземельного металла или щелочного металла, или остатки щелочного соединения; и
c) атомы фосфора,
где содержание ацетальдегида в указанных изделиях составляет менее 11 ч./млн.
23. Изделие по п.22, где изделие представляет собой преформу бутылки, изготовленную без добавления органических поглотителей ацетальдегида.
24. Изделие по п.22, где содержание ацетальдегида составляет 7 ч./млн. или менее.
25. Изделие по п.22, где гранулы содержат атомы фосфора в количестве по меньшей мере 20 ч./млн.
26. Изделие по п.22, где изделие имеет значение параметра L* по меньшей мере 70.
27. Изделие по п.22, где содержание ацетальдегида составляет 4 ч./млн. или менее.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US71828605P | 2005-09-16 | 2005-09-16 | |
US60/718,286 | 2005-09-16 | ||
US11/495,431 | 2006-07-28 | ||
US11/495,431 US7932345B2 (en) | 2005-09-16 | 2006-07-28 | Aluminum containing polyester polymers having low acetaldehyde generation rates |
Publications (2)
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RU2008114851A true RU2008114851A (ru) | 2009-10-27 |
RU2448124C2 RU2448124C2 (ru) | 2012-04-20 |
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Application Number | Title | Priority Date | Filing Date |
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RU2008114851/04A RU2448124C2 (ru) | 2005-09-16 | 2006-09-06 | Алюминийсодержащие полиэфирные полимеры, обладающие низкими скоростями образования ацетальдегида |
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US (1) | US7932345B2 (ru) |
EP (1) | EP1924628B1 (ru) |
JP (1) | JP5270350B2 (ru) |
KR (1) | KR101313416B1 (ru) |
BR (1) | BRPI0615827B1 (ru) |
CA (1) | CA2622032C (ru) |
ES (1) | ES2601183T3 (ru) |
HU (1) | HUE030251T2 (ru) |
LT (1) | LT1924628T (ru) |
MY (1) | MY145625A (ru) |
PL (1) | PL1924628T3 (ru) |
PT (1) | PT1924628T (ru) |
RU (1) | RU2448124C2 (ru) |
TW (1) | TWI412546B (ru) |
WO (1) | WO2007035256A2 (ru) |
Families Citing this family (29)
Publication number | Priority date | Publication date | Assignee | Title |
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US7300967B2 (en) * | 2004-11-12 | 2007-11-27 | Eastman Chemical Company | Polyester polymer and copolymer compositions containing metallic titanium particles |
US7262476B2 (en) * | 2004-11-30 | 2007-08-28 | Agere Systems Inc. | Semiconductor device having improved power density |
US20060122300A1 (en) * | 2004-12-07 | 2006-06-08 | Zhiyong Xia | Polyester polymer and copolymer compositions containing steel particles |
US20060222795A1 (en) * | 2005-03-31 | 2006-10-05 | Howell Earl E Jr | Polyester polymer and copolymer compositions containing particles of one or more transition metal compounds |
US8557950B2 (en) * | 2005-06-16 | 2013-10-15 | Grupo Petrotemex, S.A. De C.V. | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
US7745368B2 (en) * | 2006-07-28 | 2010-06-29 | Eastman Chemical Company | Non-precipitating alkali/alkaline earth metal and aluminum compositions made with organic hydroxyacids |
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JP2005187559A (ja) | 2003-12-25 | 2005-07-14 | Toyobo Co Ltd | ポリエステルならびにポリエステルの製造方法 |
JP2005187560A (ja) | 2003-12-25 | 2005-07-14 | Toyobo Co Ltd | ポリエステルならびにポリエステルの製造方法 |
JP2005213291A (ja) | 2004-01-27 | 2005-08-11 | Toyobo Co Ltd | ポリエステル樹脂組成物およびそれからなるポリエステル成形体 |
JP2005213293A (ja) | 2004-01-27 | 2005-08-11 | Toyobo Co Ltd | ポリエステル樹脂組成物およびそれからなるポリエステル成形体 |
JP2005213292A (ja) | 2004-01-27 | 2005-08-11 | Toyobo Co Ltd | ポリエステル樹脂組成物およびそれからなるポリエステル成形体 |
JP2005220234A (ja) | 2004-02-05 | 2005-08-18 | Toyobo Co Ltd | ポリエステル樹脂およびそれからなるポリエステル樹脂組成物並びにポリエステル成形体 |
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WO2006107373A1 (en) * | 2005-03-31 | 2006-10-12 | Exxonmobil Chemical Patents Inc. | Processes for producing high density polyethylene |
US8557950B2 (en) * | 2005-06-16 | 2013-10-15 | Grupo Petrotemex, S.A. De C.V. | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
JP3161509U (ja) | 2010-02-01 | 2010-08-05 | 横浜金属工芸株式会社 | ワ−キングチェア− |
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Also Published As
Publication number | Publication date |
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HUE030251T2 (en) | 2017-05-29 |
MY145625A (en) | 2012-03-15 |
WO2007035256A8 (en) | 2007-06-14 |
CA2622032A1 (en) | 2007-03-29 |
BRPI0615827B1 (pt) | 2019-04-02 |
RU2448124C2 (ru) | 2012-04-20 |
WO2007035256A3 (en) | 2007-11-22 |
US20070066791A1 (en) | 2007-03-22 |
WO2007035256A2 (en) | 2007-03-29 |
JP2009508990A (ja) | 2009-03-05 |
PT1924628T (pt) | 2016-11-25 |
PL1924628T3 (pl) | 2017-08-31 |
EP1924628B1 (en) | 2016-08-17 |
CA2622032C (en) | 2012-07-10 |
US7932345B2 (en) | 2011-04-26 |
JP5270350B2 (ja) | 2013-08-21 |
EP1924628A4 (en) | 2010-11-24 |
KR20080049048A (ko) | 2008-06-03 |
TWI412546B (zh) | 2013-10-21 |
LT1924628T (lt) | 2016-12-12 |
KR101313416B1 (ko) | 2013-10-01 |
EP1924628A2 (en) | 2008-05-28 |
ES2601183T3 (es) | 2017-02-14 |
BRPI0615827A2 (pt) | 2011-05-24 |
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