JP6018362B2 - 修飾クロム系触媒およびそれを用いる重合方法 - Google Patents
修飾クロム系触媒およびそれを用いる重合方法 Download PDFInfo
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- JP6018362B2 JP6018362B2 JP2010548653A JP2010548653A JP6018362B2 JP 6018362 B2 JP6018362 B2 JP 6018362B2 JP 2010548653 A JP2010548653 A JP 2010548653A JP 2010548653 A JP2010548653 A JP 2010548653A JP 6018362 B2 JP6018362 B2 JP 6018362B2
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- Prior art keywords
- catalyst
- chromium
- chromate
- flow index
- bis
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- 239000003054 catalyst Substances 0.000 title claims description 335
- 238000006116 polymerization reaction Methods 0.000 title claims description 69
- 238000000034 method Methods 0.000 title claims description 65
- 150000001844 chromium Chemical class 0.000 title 1
- 239000011651 chromium Substances 0.000 claims description 139
- 229910052804 chromium Inorganic materials 0.000 claims description 112
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 111
- 230000004044 response Effects 0.000 claims description 106
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 101
- 239000003638 chemical reducing agent Substances 0.000 claims description 92
- 239000000203 mixture Substances 0.000 claims description 75
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 claims description 71
- 239000000377 silicon dioxide Substances 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 45
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 43
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 42
- CQBWEBXPMRPCSI-UHFFFAOYSA-M O[Cr](O[SiH3])(=O)=O Chemical compound O[Cr](O[SiH3])(=O)=O CQBWEBXPMRPCSI-UHFFFAOYSA-M 0.000 claims description 38
- -1 chromium halide Chemical class 0.000 claims description 38
- 238000013019 agitation Methods 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 26
- 229920000098 polyolefin Polymers 0.000 claims description 22
- 150000001336 alkenes Chemical class 0.000 claims description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- AQLZCGLPNYEIDH-UHFFFAOYSA-N C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[Cr](=O)(=O)O[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[Cr](=O)(=O)O[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 AQLZCGLPNYEIDH-UHFFFAOYSA-N 0.000 claims description 8
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 8
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- UMJCFHSRYBYEOJ-UHFFFAOYSA-N C1=CC=C2C([Si](C=3C4=CC=CC=C4C=CC=3)(C=3C4=CC=CC=C4C=CC=3)O[Cr](=O)(O[Si](C=3C4=CC=CC=C4C=CC=3)(C=3C4=CC=CC=C4C=CC=3)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 Chemical compound C1=CC=C2C([Si](C=3C4=CC=CC=C4C=CC=3)(C=3C4=CC=CC=C4C=CC=3)O[Cr](=O)(O[Si](C=3C4=CC=CC=C4C=CC=3)(C=3C4=CC=CC=C4C=CC=3)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 UMJCFHSRYBYEOJ-UHFFFAOYSA-N 0.000 claims description 3
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 claims description 2
- RZZDGFXBQNRTBZ-UHFFFAOYSA-N C=1C=CC=CC=1C[Si](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)O[Cr](=O)(=O)O[Si](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C[Si](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)O[Cr](=O)(=O)O[Si](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 RZZDGFXBQNRTBZ-UHFFFAOYSA-N 0.000 claims description 2
- PSTSCESDKPUCIO-UHFFFAOYSA-M CC(C=CC=C1)=C1[SiH2][SiH](O[Cr](O)(=O)=O)[SiH2]C1=C(C)C=CC=C1 Chemical compound CC(C=CC=C1)=C1[SiH2][SiH](O[Cr](O)(=O)=O)[SiH2]C1=C(C)C=CC=C1 PSTSCESDKPUCIO-UHFFFAOYSA-M 0.000 claims description 2
- FAWSHMBMQYPQOH-UHFFFAOYSA-N CCCC[Si](CCCC)(CCCC)O[Cr](=O)(=O)O[Si](CCCC)(CCCC)CCCC Chemical compound CCCC[Si](CCCC)(CCCC)O[Cr](=O)(=O)O[Si](CCCC)(CCCC)CCCC FAWSHMBMQYPQOH-UHFFFAOYSA-N 0.000 claims description 2
- OJIUNXJACHBZCU-UHFFFAOYSA-N CC[Si](CC)(CC)O[Cr](=O)(=O)O[Si](CC)(CC)CC Chemical compound CC[Si](CC)(CC)O[Cr](=O)(=O)O[Si](CC)(CC)CC OJIUNXJACHBZCU-UHFFFAOYSA-N 0.000 claims description 2
- GYEFIJWMVDUNSH-UHFFFAOYSA-N Cc1c(C)c([SiH2]O[Cr](=O)(=O)O[SiH2]c2c(C)c(C)c(C)c3ccccc23)c2ccccc2c1C Chemical compound Cc1c(C)c([SiH2]O[Cr](=O)(=O)O[SiH2]c2c(C)c(C)c(C)c3ccccc23)c2ccccc2c1C GYEFIJWMVDUNSH-UHFFFAOYSA-N 0.000 claims description 2
- UVWPJSOTFPUSKM-UHFFFAOYSA-M O[Cr](O[SiH](CC(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)CC(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)(=O)=O Chemical compound O[Cr](O[SiH](CC(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)CC(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)(=O)=O UVWPJSOTFPUSKM-UHFFFAOYSA-M 0.000 claims description 2
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- LDYLHMQUPCBROZ-UHFFFAOYSA-N diethyl(methoxy)alumane Chemical compound [O-]C.CC[Al+]CC LDYLHMQUPCBROZ-UHFFFAOYSA-N 0.000 claims description 2
- MSJGTVVKAYQMPX-UHFFFAOYSA-N diethyl(propoxy)alumane Chemical compound CCC[O-].CC[Al+]CC MSJGTVVKAYQMPX-UHFFFAOYSA-N 0.000 claims description 2
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 claims description 2
- ROEOBAPIAYSJDQ-UHFFFAOYSA-N ethanolate;ethyl(methyl)alumanylium Chemical compound CC[O-].CC[Al+]C ROEOBAPIAYSJDQ-UHFFFAOYSA-N 0.000 claims description 2
- XGAIERUWZADBAO-UHFFFAOYSA-N ethoxy-bis(2-methylpropyl)alumane Chemical compound CCO[Al](CC(C)C)CC(C)C XGAIERUWZADBAO-UHFFFAOYSA-N 0.000 claims description 2
- UYONORMOFAZUJY-UHFFFAOYSA-N ethoxy-di(propan-2-yl)alumane Chemical compound CC[O-].CC(C)[Al+]C(C)C UYONORMOFAZUJY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 1
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- 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
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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
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49345—Catalytic device making
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (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)
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| WO2010074994A1 (en) * | 2008-12-22 | 2010-07-01 | Univation Technologies, Llc | Systems and methods for fabricating polymers |
| CN102372796B (zh) * | 2010-08-12 | 2013-04-24 | 中国石油化工股份有限公司 | 硅胶负载型复合铬系催化剂及其制备方法和应用 |
| EP2447290A1 (en) | 2010-11-01 | 2012-05-02 | Ineos Commercial Services UK Limited | Chromium catalysed ethylene copolymer powder |
| CN102952221A (zh) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | 用于铬系聚乙烯催化剂制备方法 |
| MX352923B (es) | 2012-05-09 | 2017-12-14 | Sasol Tech Pty Ltd | Oligomerizacion de compuestos olefinicos con menor formacion de polimeros. |
| IN2015DN02467A (enExample) | 2012-11-01 | 2015-09-04 | Univation Tech Llc | |
| CN104004117A (zh) * | 2013-02-27 | 2014-08-27 | 中国石油化工股份有限公司 | 气相法高密度聚乙烯的聚合方法 |
| JP6187332B2 (ja) * | 2013-03-28 | 2017-08-30 | 日本ポリエチレン株式会社 | パイプ及び継手用ポリエチレン並びにその成形体 |
| CA2909935C (en) | 2013-05-02 | 2021-01-26 | Dow Global Technologies Llc | A polyethylene composition and articles made therefrom |
| BR112016010838B1 (pt) | 2013-11-21 | 2022-05-03 | Univation Technologies, Llc | Método para produzir poliolefinas |
| SG10202001312WA (en) | 2014-09-02 | 2020-04-29 | Univation Tech Llc | Polyolefin production with chromium-based catalysts |
| CN106795240B (zh) * | 2014-09-02 | 2020-06-23 | 尤尼威蒂恩技术有限责任公司 | 使用铬类催化剂的聚烯烃制造 |
| ES3041028T3 (en) * | 2014-09-02 | 2025-11-06 | Univation Tech Llc | Polyolefin production with chromium-based catalysts |
| CN107001516B (zh) | 2014-11-24 | 2023-06-06 | 尤尼威蒂恩技术有限责任公司 | 用于烯烃聚合的铬基催化剂组合物 |
| WO2017034659A1 (en) * | 2015-08-21 | 2017-03-02 | Exxonmobil Chemical Patents Inc. | Lubricant base stock blends |
| RU2739839C2 (ru) | 2016-01-29 | 2020-12-28 | ЮНИВЕЙШН ТЕКНОЛОДЖИЗ, ЭлЭлСи | Полиолефиновая пленка с улучшенной ударной прочностью |
| KR102220684B1 (ko) * | 2016-11-18 | 2021-03-02 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | 크롬 함유 촉매를 이용한 중합 방법 |
| WO2018175071A1 (en) | 2017-03-21 | 2018-09-27 | Exxonmobil Chemical Patents Inc. | Processes for preparing a catalyst system and polymerizing olefins |
| EP3601378A1 (en) | 2017-03-23 | 2020-02-05 | ExxonMobil Chemical Patents Inc. | Catalyst systems and methods for preparing and using the same |
| US11161924B2 (en) | 2017-10-27 | 2021-11-02 | Univation Technologies, Llc | Polyethylene copolymer resins and films |
| US11161923B2 (en) | 2017-10-27 | 2021-11-02 | Univation Technologies, Llc | Selectively transitioning polymerization processes |
| SG11202001743RA (en) | 2017-10-31 | 2020-05-28 | Exxonmobil Chemical Patents Inc | Toluene free silica supported single-site metallocene catalysts from in-situ supported alumoxane formation in aliphatic solvents |
| WO2019226344A1 (en) | 2018-05-24 | 2019-11-28 | Univation Technologies, Llc | Unimodal polyethylene copolymer and film thereof |
| SG11202100284XA (en) | 2018-07-31 | 2021-03-30 | Univation Tech Llc | Unimodal polyethylene copolymer and film thereof |
| CN112739731A (zh) | 2018-07-31 | 2021-04-30 | 尤尼威蒂恩技术有限责任公司 | 单峰聚乙烯共聚物和其膜 |
| US12152095B2 (en) | 2019-03-21 | 2024-11-26 | Exxonmobil Chemical Patents Inc. | Methods for improving production in gas phase polymerization |
| EP3941949B1 (en) | 2019-03-21 | 2025-10-22 | ExxonMobil Chemical Patents Inc. | Methods for improving gas phase polymerization |
| CA3142138A1 (en) | 2019-06-10 | 2020-12-17 | Univation Technologies, Llc | Polyethylene blend |
| CN114787208A (zh) | 2019-12-11 | 2022-07-22 | 埃克森美孚化学专利公司 | 低芳香性的聚烯烃 |
| CN115989275B (zh) | 2020-08-25 | 2025-03-25 | 埃克森美孚化学专利公司 | 具有优异物理性能的高密度聚乙烯组合物 |
| EP4247819A1 (en) | 2020-11-23 | 2023-09-27 | ExxonMobil Chemical Patents Inc. | Toluene free supported methylalumoxane precursor |
| WO2022108972A1 (en) | 2020-11-23 | 2022-05-27 | Exxonmobil Chemical Patents Inc. | Improved process to prepare catalyst from in-situ formed alumoxane |
| WO2022250822A1 (en) | 2021-05-24 | 2022-12-01 | Exxonmobil Chemical Patents Inc. | Biphasic polymerization processes |
| EP4416198A1 (en) | 2021-10-15 | 2024-08-21 | Univation Technologies LLC | Hdpe intermediate bulk container resin using advanced chrome catalyst by polyethylene gas phase technology |
| CN118103416A (zh) | 2021-10-15 | 2024-05-28 | 尤尼威蒂恩技术有限责任公司 | 通过聚乙烯气相技术使用高级铬催化剂的hdpe lpbm树脂 |
| JP2025525402A (ja) | 2022-06-24 | 2025-08-05 | エクソンモービル ケミカル パテンツ インコーポレイテッド | インサイチュｍａｏ担持の低コスト製法及び誘導される完成ポリオレフィン触媒 |
| WO2024253830A1 (en) | 2023-06-06 | 2024-12-12 | ExxonMobil Technology and Engineering Company | Non-coordinated alkylaluminum free cation modified alumoxanes and methods thereof |
| WO2024253831A1 (en) | 2023-06-06 | 2024-12-12 | ExxonMobil Technology and Engineering Company | Non-coordinated alkylaluminum free anion modified alumoxanes and methods thereof |
| US12319774B1 (en) | 2024-01-23 | 2025-06-03 | Chevron Phillips Chemical Company Lp | Particle size control of silyl chromate catalysts and uses thereof in fluidized bed reactors |
| WO2025250307A1 (en) | 2024-05-30 | 2025-12-04 | ExxonMobil Technology and Engineering Company | Methods for improving gas phase polymerization |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4356294A (en) * | 1980-10-24 | 1982-10-26 | National Petro Chemicals Corp. | Production of polyolefins having improved ESCR |
| US4543399A (en) * | 1982-03-24 | 1985-09-24 | Union Carbide Corporation | Fluidized bed reaction systems |
| FR2572082B1 (fr) * | 1984-10-24 | 1987-05-29 | Bp Chimie Sa | Procede de demarrage de polymerisation d'ethylene ou de copolymerisation d'ethylene et d'alpha-olefine en phase gazeuse en presence de catalyseur a base d'oxyde de chrome |
| WO1994013708A1 (en) * | 1992-12-17 | 1994-06-23 | Neste Oy | Process for the polymerization of ethylene by a catalyst which contains chromium and an ethylene polymer obtained by this process |
| BE1008916A3 (fr) * | 1994-11-16 | 1996-10-01 | Solvay | Systeme catalytique pour la polymerisation d'olefines et procede de polymerisation d'au moins une olefine en presence de ce systeme catalytique. |
| WO1998046653A1 (en) * | 1997-04-11 | 1998-10-22 | Showa Denko K. K. | Process for preparing ethylene polymer and catalyst used therefor |
| US5856257A (en) * | 1997-05-16 | 1999-01-05 | Phillips Petroleum Company | Olefin production |
| CN1095475C (zh) | 1997-10-13 | 2002-12-04 | 中国石化齐鲁石油化工公司 | 一种适用于气相法乙烯聚合工艺的负载型催化剂及其制备方法 |
| JP2001294612A (ja) | 2000-04-10 | 2001-10-23 | Asahi Kasei Corp | オレフィン重合用触媒および重合方法。 |
| EP1172381A1 (en) * | 2000-07-07 | 2002-01-16 | Japan Polyolefins Co., Ltd. | Ethylene polymers and method for producing the same |
| JP4610051B2 (ja) | 2000-07-07 | 2011-01-12 | 日本ポリオレフィン株式会社 | エチレン系重合用触媒、エチレン系重合体およびその製造方法 |
| US6989344B2 (en) * | 2002-12-27 | 2006-01-24 | Univation Technologies, Llc | Supported chromium oxide catalyst for the production of broad molecular weight polyethylene |
| ATE435244T1 (de) * | 2003-03-28 | 2009-07-15 | Union Carbide Chem Plastic | Katalysatoren basiert auf chrom in einem mineralöl und verfahren zur polymerisation von ethylen |
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- 2008-12-10 WO PCT/US2008/013547 patent/WO2009108174A1/en not_active Ceased
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- 2008-12-10 CN CN2008801261016A patent/CN101932617B/zh active Active
- 2008-12-18 TW TW097149464A patent/TWI449718B/zh not_active IP Right Cessation
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| EP2247630B1 (en) | 2016-02-24 |
| ES2568043T3 (es) | 2016-04-27 |
| EP2247630A1 (en) | 2010-11-10 |
| CN101932617B (zh) | 2012-10-03 |
| US9303103B2 (en) | 2016-04-05 |
| JP2011513533A (ja) | 2011-04-28 |
| WO2009108174A1 (en) | 2009-09-03 |
| TWI449718B (zh) | 2014-08-21 |
| TW200940574A (en) | 2009-10-01 |
| CN101932617A (zh) | 2010-12-29 |
| US20110010938A1 (en) | 2011-01-20 |
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