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研究生： 陳秉彥
Ping-Yen Chen
論文名稱： 新型氫氧根離子交換膜之製備及性質探討
Synthesis and Characterization of Novel Hydroxide Exchange Membranes
指導教授： 陳志堅
Jyh-Chien Chen
口試委員: 王英靖
Ing-Jing Wang
游進陽
Chin-Yang Yu
劉貴生
Guey-Sheng Liou
蕭勝輝
Sheng-Huei Hsiao
學位類別： 博士
Doctor
系所名稱： 工程學院 - 材料科學與工程系
Department of Materials Science and Engineering
論文出版年： 2018
畢業學年度： 106
語文別： 英文
論文頁數： 161
中文關鍵詞： 氫氧根離子交換膜 、聚醚砜 、聚苯并咪唑 、四級銨陽離子 、氫氧根傳導率 、鹼性穩定性
外文關鍵詞： hydroxide exchange membrane, polyethersulfone, polybenzimidazole, quaternary ammonium cation, hydroxide conductivity, alkaline stability
相關次數： 點閱：190  下載：1 
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    • 本研究包含三個章節。氫氧根離子交換膜之研究背景、近來發展及現今挑戰的相關文獻將在第一章中回顧。關於”具有密集四級銨基團之聚醚砜氫氧根離子交換膜”及”藉Click化學反應製備之交聯聚苯并咪唑氫氧根離子交換膜”之研究則分別在第二章及第三章探討。
    在第二章中，為了提升薄膜之性質，我們製備具有密集四級銨基團之聚醚砜氫氧根離子交換膜。在聚醚砜上導入官能基時，數個合成障礙已成功被克服。所製備的氫氧根離子交換膜之性質已被測量，如離子含量、吸水率、尺寸變化、熱穩定性、拉伸強度、氫氧根傳導率、薄膜型態及鹼性穩定性。我們發現當陽離子在氫氧根離子交換膜中較聚集時，薄膜可以吸收較少的水卻展現較高的氫氧根傳導率。顯著的薄膜微相分離所造成較大且連續的親水區可助於加速氫氧根的傳遞。我們藉由檢視40MePh-1.72及50MePh-1.99離子含量及氫氧根傳導率變化評估其鹼性穩定性。在720小時鹼性穩定性測試後，其離子含量及氫氧根傳導率仍維持原有的70 %以上。
    在第三章中，我們將製備及改質聚醚酚苯并咪唑(poly(oxyphenylene benzimidazole))。起初我們打算在重複單元中每個咪唑環進行兩次有機烃的接枝反應，將咪唑環離子化，形成咪唑陽離子環。其中，接枝於咪唑環的末端烯或炔作為可交聯之官能基。然而，我們發現咪唑陽離子在鹼性環境下相當不穩定。因此，我們利用另一種方式在高分子鏈上導入陽離子基團。藉由相同的合成方法，部分的咪唑環被5-(三甲基銨溴)戊烷進行一次取代反應但未離子化，剩餘咪唑環則由丙烯基或丙炔基取代。藉由調控反應溫度及接枝劑的進藥量，可以調整5-(三甲基銨溴)戊烷及丙烯基/丙炔基不同的取代比例。由丙烯基及丙烯炔取代的交聯薄膜分別透過硫醇-烯及疊氮-炔反應製備而成。薄膜的交聯程度由凝膠比率表示，其皆高於90 %。交聯及未交聯薄膜的特性已被表徵及比較，例如:離子含量、吸水率、尺寸變化、氫氧根傳導率、薄膜型態、熱穩定性及拉伸強度。具有最多離子對的未交聯薄膜浸泡60及80 oC之1 M氫氧化鈉水溶液中21天後，其結構經由氫核磁共振光譜分析並未顯示任何改變。甚者，其結構經過80 oC之2及4 M氫氧化鈉水溶液浸泡21天後仍維持穩定。

    This dissertation includes three chapters. Literatures about the background, development and challenges of hydroxide exchange membranes are reviewed in Chapter 1. The studies with a topic of “Polyethersulfone-based Hydroxide Exchange Membrane Containing Dense Quaternary Ammonium Cations” and “Crosslinked Polybenzimidazole-based Hydroxide Exchange Membrane via Click Chemistry Reaction” are involved in Chapter 2 and Chapter 3, respectively.
    In Chapter 2, polyethersulfone-based hydroxide exchange membranes containing dense quaternary ammonium cations were prepared in order to improve the properties of the membranes. Several barriers of synthesis of functionalized polyethersulfones were overcome. The properties of prepared HEMs, such as IEC, water uptake, dimensional change, thermal stability, tensile strength, hydroxide conductivity, membrane morphology and alkaline stability, have been evaluated. We found that HEMs tethering with cationic groups locating closely together seem to absorb less water uptake but exhibit higher hydroxide conductivity. Obvious microphase separation of membrane morphology leading to larger and continuous domains of hydrophilic cationic groups can be found which boosts the transport of hydroxide. The alkaline stability of 40MePh-1.72 and 50MePh-1.99 was investigated by monitoring the change of IEC and hydroxide conductivity. Their IEC and hydroxide conductivity still remains higher than 70 % of the original one after alkaline stability test for 720 h.
    In Chapter 3, we synthesized and functionalized poly(oxyphenylene benzimidazole). Initially, we intended to ionized the imidazole rings in the repeating units to form imidazolium cations via twice grafting alkyl groups on each imidazole ring. The imidazole rings were substituted with alkene or alkyne as crosslinkable functional groups. Nevertheless, we found that the structures are unstable in the alkaline environment. Therefore, introducing the cationic groups onto the PBIs based on another strategy was carried out. By using the same synthetic method, partial imidazole rings of PBI were instead grafted by 5-(trimethylammonium- bromide)pentyl once but not ionized, and the other residual imidazole rings were substituted with allyl or propargyl group. Various grafting ratio of 5-(trimethylammoniumbromide)pentyl and allyl/propargyl groups could be adjusted by controlling reaction temperature and fed amount of the grafting reagent. Crosslinked membranes of the PBIs grafted with allyl and propargyl groups were then fabricated via “click” thiol-ene reaction and azide-alkyne cycloaddition, respectively. The gel fractions of all crosslinked membranes are higher than 90 %. The properties of crosslinked and uncrosslinked membranes, such as IEC, water uptake, dimensional change, hydroxide conductivity, morphology, thermal stability and tensile properties, were characterized and compared. The uncrosslinked membrane possessing the most ion pairs was soaked in 1 M NaOH aqueous solution at 60 and 80 oC for 21 days. The structure was analyzed by 1H NMR spectroscope showing no apparent change. Moreover, the structure still remains stable even when soaked in higher concentration of alkaline solution (2 and 4 M) at 80 oC for 21 days.

    Content 中文摘要 i Abstract iii Acknowledgements v Content vi List of Figures x List of Schemes xiv List of Tables xvii Preface xviii Chapter 1 Introduction and literature review 1 1.1 Proton exchange membrane fuel cells (PEMFCs) 4 1.1.1 Low-temperature PEMFCs 4 1.1.2 High-temperature PEMFCs 6 1.2 Hydroxide exchange membrane fuel cells (HEMFCs) 12 1.2.1 The history of alkaline fuel cells (AFCs) 12 1.2.2 The types of materials as hydroxide exchange membrane 14 1.2.2.1 Polymer backbone 14 1.2.2.1.1 HEMs based on polyvinyl types polymer 15 1.2.2.1.2 HEMs based on polyethersulfones/polyetherketones 18 1.2.2.1.3 HEMs based on PPOs 21 1.2.2.1.4 HEMs based on polybenzimidazole (PBI) 22 1.2.2.1.5 HEMs based on special polymer structures 24 1.2.2.2 Fixed ion pair 26 1.2.2.3 Approaches to join polymer and ion pair 27 1.2.2.3.1 HEMs based on block copolymer architecture 29 1.2.2.3.2 HEMs tethered with a spacer, extender or separate alkyl chain 31 1.2.2.3.3 HEMs grafted with multi-cations 37 1.2.3 Alkaline stability and possible degradation of HEMs 39 1.2.3.1 The alkaline stability of cationic groups 40 1.2.3.2 The alkaline stability of polymer backbone 46 1.2.4 The mechanism of hydroxide transport in HEMs 50 Chapter 2 Polyethersulfone-based Hydroxide Exchange Membrane Containing Dense Quaternary Ammonium Cations 55 Abstract 56 2.1 Background and motivation 57 2.2 Experimental 63 2.2.1 Measurements 63 2.2.2 Materials 64 2.2.3 Monomer synthesis 65 2.2.4 Preparation of hydroxide exchange membrane 69 2.2.5 Membrane properties 72 2.3 Results and Discussion 74 2.3.1 Monomer synthesis 74 2.3.2 Synthesis of polyethersulfones, XPh and XMePh 77 2.3.3 Chloromethylated XPh and brominated XMePh 79 2.3.4 Structural assignment of XMePh-YBr and XMePh-Z 86 2.3.5 Characterization of membrane properties 88 2.3.5.1 Ion exchange capacities (IECs), water uptake, dimensional change and hydroxide conductivity 88 2.3.5.2 Thermal stability and mechanical strength of XMePh-Z 93 2.3.5.3 Membrane morphology 96 2.3.5.4 Alkaline stability 99 2.4 Conclusions 101 Chapter 3 Crosslinked Polybenzimidazole-based Hydroxide Exchange Membrane via Click Chemistry Reaction 102 Abstract 103 3.1 Background and motivation 105 3.2 Experimental 110 3.2.1 Measurements 110 3.2.2 Materials 110 3.2.3 Synthesis of poly(oxyphenylene benzimidazole) (OPBI) 111 3.2.4 Grafted OPBI with various substituents on imidazole ring 112 3.2.5 The 2nd step of grafting reaction of 49%Me-OPBI, 47%Pr-OPBI, 49%Py-OPBI and 45%VBz-OPBI 115 3.2.6 Crosslinked membrane fabrication through “click” chemistry reaction 116 3.2.7 Membrane properties 117 3.3 Results and discussion 120 3.3.1 Synthesis and structural characterization of poly(oxyphenylene benzimidazole) (OPBI) 120 3.3.2 Synthesis and structural characterization of functionalized OPBIs 121 3.3.3 The change of functionalized OPBI after ion exchange procedure 125 3.3.4 Synthesis and structural characterization of 5-(trimethylammonium- bromide)pentyl-grafted OPBI 128 3.3.5 Characterization of membrane properties 132 3.3.5.1 Ion exchange capacities (IECs), water uptake, dimensional change, gel fraction and hydroxide conductivity 132 3.3.5.2 Thermal stability and mechanical strength 135 3.3.5.3 Membrane morphology 139 3.3.5.4 Alkaline stability 142 3.4 Conclusions 146 Perspective and future works 147 References 148

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