RU2011129234A - Способ обработки зародышевого слоя реакции полимеризации - Google Patents
Способ обработки зародышевого слоя реакции полимеризации Download PDFInfo
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- RU2011129234A RU2011129234A RU2011129234/04A RU2011129234A RU2011129234A RU 2011129234 A RU2011129234 A RU 2011129234A RU 2011129234/04 A RU2011129234/04 A RU 2011129234/04A RU 2011129234 A RU2011129234 A RU 2011129234A RU 2011129234 A RU2011129234 A RU 2011129234A
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- germ layer
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- polymerization reaction
- organometallic compound
- reactor
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- 238000000034 method Methods 0.000 title claims abstract 24
- 238000006116 polymerization reaction Methods 0.000 title claims abstract 10
- 210000001654 germ layer Anatomy 0.000 claims abstract 14
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract 7
- 239000000203 mixture Substances 0.000 claims abstract 6
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract 5
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract 4
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000002245 particle Substances 0.000 claims abstract 4
- 229920000642 polymer Polymers 0.000 claims abstract 4
- QQTGJVBUIOTPGZ-UHFFFAOYSA-N CCC[Zn]CCC Chemical compound CCC[Zn]CCC QQTGJVBUIOTPGZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract 2
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052744 lithium Inorganic materials 0.000 claims abstract 2
- 229910052749 magnesium Inorganic materials 0.000 claims abstract 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052708 sodium Inorganic materials 0.000 claims abstract 2
- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 claims abstract 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims abstract 2
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims abstract 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims abstract 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims abstract 2
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 claims abstract 2
- WSITXTIRYQMZHM-UHFFFAOYSA-N tris(4-methylphenyl)alumane Chemical compound C1=CC(C)=CC=C1[Al](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSITXTIRYQMZHM-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052725 zinc Inorganic materials 0.000 claims abstract 2
- 239000000178 monomer Substances 0.000 claims 5
- 150000001336 alkenes Chemical class 0.000 claims 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 4
- 239000000654 additive Substances 0.000 claims 3
- 230000000996 additive effect Effects 0.000 claims 3
- 239000003054 catalyst Substances 0.000 claims 3
- 230000003197 catalytic effect Effects 0.000 claims 3
- 229910052751 metal Inorganic materials 0.000 claims 3
- 239000002184 metal Substances 0.000 claims 3
- 229920000098 polyolefin Polymers 0.000 claims 3
- 150000007942 carboxylates Chemical class 0.000 claims 2
- 239000007789 gas Substances 0.000 claims 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 1
- VUNJVVRGYQSNQB-UHFFFAOYSA-N CCCC[Zn] Chemical compound CCCC[Zn] VUNJVVRGYQSNQB-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims 1
- 229940083916 aluminum distearate Drugs 0.000 claims 1
- 229940063655 aluminum stearate Drugs 0.000 claims 1
- RDIVANOKKPKCTO-UHFFFAOYSA-K aluminum;octadecanoate;hydroxide Chemical compound [OH-].[Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O RDIVANOKKPKCTO-UHFFFAOYSA-K 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 239000012968 metallocene catalyst Substances 0.000 claims 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 238000010926 purge Methods 0.000 claims 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 claims 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000004711 α-olefin Substances 0.000 claims 1
- -1 tripylaluminum Chemical compound 0.000 abstract 4
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 abstract 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 abstract 1
- ISEJRLXHKSHKPM-UHFFFAOYSA-N dimethyl(2-methylpropyl)alumane Chemical compound CC(C)C[Al](C)C ISEJRLXHKSHKPM-UHFFFAOYSA-N 0.000 abstract 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 abstract 1
- LOAHJABDATVOQU-UHFFFAOYSA-N ethyl(methyl)alumane Chemical compound C[AlH]CC LOAHJABDATVOQU-UHFFFAOYSA-N 0.000 abstract 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 abstract 1
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 abstract 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 abstract 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 abstract 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 abstract 1
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 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
- 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
- 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
-
- 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
- Y10S526/901—Monomer polymerized in vapor state in presence of transition metal containing catalyst
-
- 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
- Y10S526/905—Polymerization in presence of transition metal containing catalyst in presence of hydrogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
1. Способ подготовки реактора к проведению реакции полимеризации, включающий обеспечение в реакторе по меньшей мере одного зародышевого слоя; причем по меньшей мере один зародышевый слой включает по меньшей мере одно металлоорганическое соединение и частицы полимера, и причем зародышевый слой дополнительно контактирует по меньшей мере с одним углеводородом, так, что, по меньшей мере, один углеводород присутствует в газовой фазе зародышевого слоя в количестве от 2 до 8 мол.%.2. Способ по п.1, в котором по меньшей мере одно металлоорганическое соединение представляют формулойMR,в которой М представляет собой атом элемента групп 1, 2, 12 и 13; R независимо выбирают из Cалкенилов, Cалкильной группы, Cалкоксилов, Cарильных групп, алкиларильных групп, Cциклопентадиенилов и смесей из двух или более перечисленных компонентов; и а представляет собой валентное состояние, достаточное, чтобы уравновесить М.3. Способ по п.2, в котором М представляет собой Mg, Zn, Li, Al, Na или K.4. Способ по п.1, в котором по меньшей мере одно металлоорганическое соединение включает триизобутилалюминий, трипропилалюминий, трибутилалюминий, диметилхлоралюминий, диметилизобутилалюминий, диметилэтилалюминий, диэтилхлоралюминий, триизопропилалюминий, три-s-бутилалюминий, трициклопентилалюминий, трипентилалюминий, триизопентилалюминий, тригексилалюминий, этилдиметилалюминий, метилдиэтилалюминий, трифенилалюминий, три-п-толилалюминий, диметилалюминийметоксид, диметилалюмипийметоксид, метиллитий, бутиллитий, ди-н-пропилцинк, ди-н-бутилцинк, диэтилцинк, триметилбор, триэтилбор, триизобутилбор, трипропилбор, трибутилбор или смеси перечисленного.5. Способ по
Claims (18)
1. Способ подготовки реактора к проведению реакции полимеризации, включающий обеспечение в реакторе по меньшей мере одного зародышевого слоя; причем по меньшей мере один зародышевый слой включает по меньшей мере одно металлоорганическое соединение и частицы полимера, и причем зародышевый слой дополнительно контактирует по меньшей мере с одним углеводородом, так, что, по меньшей мере, один углеводород присутствует в газовой фазе зародышевого слоя в количестве от 2 до 8 мол.%.
2. Способ по п.1, в котором по меньшей мере одно металлоорганическое соединение представляют формулой
MaR,
в которой М представляет собой атом элемента групп 1, 2, 12 и 13; R независимо выбирают из C1-20алкенилов, C1-20алкильной группы, C1-20алкоксилов, C6-20арильных групп, алкиларильных групп, C5-25циклопентадиенилов и смесей из двух или более перечисленных компонентов; и а представляет собой валентное состояние, достаточное, чтобы уравновесить М.
3. Способ по п.2, в котором М представляет собой Mg, Zn, Li, Al, Na или K.
4. Способ по п.1, в котором по меньшей мере одно металлоорганическое соединение включает триизобутилалюминий, трипропилалюминий, трибутилалюминий, диметилхлоралюминий, диметилизобутилалюминий, диметилэтилалюминий, диэтилхлоралюминий, триизопропилалюминий, три-s-бутилалюминий, трициклопентилалюминий, трипентилалюминий, триизопентилалюминий, тригексилалюминий, этилдиметилалюминий, метилдиэтилалюминий, трифенилалюминий, три-п-толилалюминий, диметилалюминийметоксид, диметилалюмипийметоксид, метиллитий, бутиллитий, ди-н-пропилцинк, ди-н-бутилцинк, диэтилцинк, триметилбор, триэтилбор, триизобутилбор, трипропилбор, трибутилбор или смеси перечисленного.
5. Способ по любому из предшествующих пунктов, в котором по меньшей мере одно металлоорганическое соединение присутствует в зародышевом слое в количестве от 25 до 250 мас.ч./млн. в расчете на общую массу зародышевого слоя.
6. Способ по п.1, в котором углеводород включает изопентан.
7. Способ по п.1, в котором зародышевый слой дополнительно контактирует с по меньшей мере одной добавкой для повышения сплошности, причем добавка для повышения сплошности включает карбоксилат металла, смешанную композицию, содержащую амин или смеси перечисленного.
8. Способ по п.7, в котором карбоксилат металла представляет собой стеарат металла, выбранный из стеарата алюминия и дистеарата алюминия.
9. Способ по п.7 или 8, в котором содержание по меньшей мере одной добавки для повышения сплошности в зародышевом слое составляет от 20 до 40 мас.ч./млн. в расчете на общую массу зародышевого слоя.
10. Способ, включающий контактирование зародышевого слоя по п.1 с каталитической системой и одним или более олефиновым мономером с целью проведения реакции полимеризации в по меньшей мере одном реакторе с получением полиолефинового продукта.
11. Способ по п.10, в котором олефиновые мономеры включают этилен и один или более из C3-C18альфа-олефиновых мономеров.
12. Способ по п.10, который дополнительно включает контактирование зародышевого слоя, каталитической системы и одного или более олефиновых мономеров с водородом.
13. Способ по п.10, в котором каталитическая система включает по меньшей мере один металлоценовый катализатор.
14. Способ по любому из пп.10-13, в котором зародышевый слой изготовлен из частиц полимера, которые приготовлены с использованием другой каталитической системы и/или при других условиях полимеризации по сравнению с полиолефиновым продуктом.
15. Способ по любому из пп.10-13, в котором зародышевый слой изготовлен из частиц полимера, которые приготовлены с использованием той же каталитической системы и/или тех же условий полимеризации, что и полиолефиновый продукт.
16. Способ по любому из пп.10-13, в котором зародышевый слой подвергают стадии продувки инертным газом до инициирования реакции полимеризации.
17. Способ по любому из пп.10-13, в котором реакцию полимеризации инициируют в течение 25 мин или менее при контактировании зародышевого слоя, каталитической системы и одного или более олефиновых мономеров.
18. Способ по любому из пп.10-13, в котором реакция полимеризации протекает в присутствии зародышевого слоя, содержащего воду в количестве 7 мас.ч./млн. или выше в газовой фазе реактора полимеризации.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US20306408P | 2008-12-18 | 2008-12-18 | |
| US61/203,064 | 2008-12-18 | ||
| PCT/US2009/068439 WO2010071798A1 (en) | 2008-12-18 | 2009-12-17 | Method for seed bed treatment for a polymerization reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| RU2011129234A true RU2011129234A (ru) | 2013-01-27 |
| RU2515900C2 RU2515900C2 (ru) | 2014-05-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| RU2011129234/04A RU2515900C2 (ru) | 2008-12-18 | 2009-12-17 | Способ обработки зародышевого слоя реакции полимеризации |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US8148481B2 (ru) |
| EP (1) | EP2358767B1 (ru) |
| CN (1) | CN102257017B (ru) |
| BR (1) | BRPI0922454A2 (ru) |
| ES (1) | ES2408589T3 (ru) |
| RU (1) | RU2515900C2 (ru) |
| WO (1) | WO2010071798A1 (ru) |
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| CN102453156B (zh) * | 2010-10-22 | 2013-11-20 | 中国石油化工股份有限公司 | 在气相流化床反应器内快速启动α-烯烃聚合反应的方法 |
| US9221935B2 (en) | 2011-06-09 | 2015-12-29 | Nova Chemicals (International) S.A. | Modified phosphinimine catalysts for olefin polymerization |
| WO2014060231A1 (en) * | 2012-10-16 | 2014-04-24 | Ineos Europe Ag | Process for the production of a polymer in a gas phase fluidised bed reactor |
| CN104854138A (zh) | 2012-12-18 | 2015-08-19 | 英尼奥斯欧洲股份公司 | 用于停止和重启聚合的方法 |
| RU2016113526A (ru) | 2013-09-10 | 2017-10-16 | Инеос Юроуп Аг | Способ (со-)полимеризации олефинов |
| CN104459024B (zh) * | 2013-09-13 | 2016-07-06 | 中国石油天然气股份有限公司 | 一种评价铬系催化剂活性的方法 |
| US10471405B2 (en) * | 2015-03-24 | 2019-11-12 | Sabic Global Technologies B.V. | Continuous gas fluidized bed polymerization process |
| WO2019173030A1 (en) * | 2018-03-08 | 2019-09-12 | Exxonmobil Chemical Patents Inc. | Methods of preparing and monitoring a seed bed for polymerization reactor startup |
| WO2022109518A1 (en) * | 2020-11-17 | 2022-05-27 | Exxonmobil Chemical Patents Inc. | Gas phase reactor startup process |
| CN114621368B (zh) * | 2020-12-10 | 2023-11-28 | 中国石油天然气股份有限公司 | 乙烯气相聚合牌号切换剂及其制备方法 |
| BR112023023848A2 (pt) * | 2021-05-18 | 2024-02-20 | Basell Polyolefine Gmbh | Processo para preparar um polímero de olefina, vaso, e, método para controlar um processo de polimerização de olefinas |
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-
2009
- 2009-12-17 CN CN200980150746.8A patent/CN102257017B/zh active Active
- 2009-12-17 WO PCT/US2009/068439 patent/WO2010071798A1/en not_active Ceased
- 2009-12-17 ES ES09775498T patent/ES2408589T3/es active Active
- 2009-12-17 US US13/128,087 patent/US8148481B2/en active Active
- 2009-12-17 BR BRPI0922454A patent/BRPI0922454A2/pt not_active IP Right Cessation
- 2009-12-17 EP EP09775498A patent/EP2358767B1/en active Active
- 2009-12-17 RU RU2011129234/04A patent/RU2515900C2/ru not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| RU2515900C2 (ru) | 2014-05-20 |
| EP2358767B1 (en) | 2013-02-20 |
| CN102257017B (zh) | 2014-02-12 |
| WO2010071798A1 (en) | 2010-06-24 |
| US20110294973A1 (en) | 2011-12-01 |
| CN102257017A (zh) | 2011-11-23 |
| US8148481B2 (en) | 2012-04-03 |
| BRPI0922454A2 (pt) | 2018-05-22 |
| ES2408589T3 (es) | 2013-06-21 |
| EP2358767A1 (en) | 2011-08-24 |
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