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研究生： 童翊婷
Yi-Ting Tung
論文名稱： 以活性開環複分解反應合成含剛性及軟性嵌段之聚降冰片烯三團塊共聚物及其在陰離子交換膜燃料電池之應用
Synthesis of Triblock Polynorbornenes Containing Rigid and Flexible Segments by Living Ring-Opening Metathesis Polymerization for Anion Exchange Membrane Fuel Cell Application
指導教授： 陳志堅
Jyh-Chien Chen
口試委員: 汪昆立
Kun-Li Wang
蕭育生
Yu-Sheng Hsiao
學位類別： 碩士
Master
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： 2023
畢業學年度： 111
語文別： 中文
論文頁數： 53
中文關鍵詞： 聚降冰片烯 、活性開環附分解聚合 、三團塊共聚物 、相分離 、陰離子交換膜 、燃料電池
外文關鍵詞： Polynorbornenes, Living ring-opening metathesis polymerization, Triblock copolymer, Phase separation, Anion exchange membrane, Fuel cell
相關次數： 點閱：285  下載：3 
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    • 本實驗以降冰片烯衍生物(norbornene derivates)為主體，利用Diels -Alder反應合成含有不同側鏈之三種單體，並採用逐次添加法(sequential addition)進行活性開環複分解聚合，製備出一系列聚降冰片三團塊共聚物，使聚合物分別含有剛硬疏水、柔軟疏水及作為傳導基團所在之親水鏈段。接著將聚合物中雙鍵進行還原，並加入交聯劑N, N, N’, N’-tetramethyl-1,3-diaminepropane(TMDAP)利用澆鑄法進行薄膜製備，將薄膜進行四級銨化及離子交換程序後成功獲得陰離子交換膜，並探討聚合物結構內不同單體組成比例對於薄膜性質所造成之差異，期望透過自組裝行為進一步控制各種薄膜性質。當聚合物中剛硬疏水鏈段之比例增加時，有效抑制吸水率並改善尺寸安定性、熱穩定性、機械強度。且成功證實可透過調控高分子中剛硬/柔軟、親水/疏水鏈段之組成進一步調控膜內之微相分離情形。其中，陰離子交換膜中離子傳導率最高的膜在80 ℃相對溼度100%之量測環境下側得之離子傳導率數值可達127 mS/cm，並且表現出優異的鹼性穩定性。以上種種數據證明自組裝行為之可行性，可自由調控薄膜之尺寸安定性、熱穩定性、機械強度、相分離現象等薄膜性質。

    In this work, three norbornene derivates with different side chains were synthesized by the Diels-Alder reaction. Triblock polynorbornenes containing hydrophobic rigid segment, hydrophobic soft segment, and anion-conducting hydrophilic segment were synthesized by living ring-opening metathesis polymerization (ROMP) using sequential monomer addition. Anion exchange membranes were obtained by solution casting, followed by quaternization and ion exchange procedures. We investigate the properties of anion exchange membranes with different monomer ratios in the polymer structures. It is expected to further control the membrane properties through self-assembly behavior or the block copolymers' hydrophilic/hydrophobic, rigid/soft phase separation. When the contents of rigid hydrophobic chain segments in the polymer increase, it effectively suppresses water uptake and improves dimensional stability, thermal stability, and mechanical strength. Furthermore, we successfully demonstrate that the phase separation of the membranes resulted from their triblock structures can affect their properties. The highest ion conductivity among these anion exchange membranes measured at 80 oC with a relative humidity of 100% is as high as 127 mS/cm. The study demonstrates that the triblock polynorbornenes prepared by living ROMP can control the membrane properties such as dimensional stability, thermal stability, and mechanical strength via phase separation.

    中文摘要 Abstract 致謝 目錄 Figure 索引 Scheme 索引 Table索引 第一章 緒論 1.1 前言 1.2 燃料電池介紹 1.3 AEMFC之原理與構造 第二章 文獻回顧 2.1 陰離子交換膜之發展 2.2 陰離子交換膜之主鏈與傳導基結構 2.3 傳導原理 2.4 鹼性穩定性與降解機制 2.5 聚降冰片烯之介紹 2.6 開環複分解聚合 2.7 研究動機與目的 第三章 實驗 3.1 實驗儀器 3.2 實驗藥品 3.3 單體合成 3.3.1 exo-1,4,4a,9,9a,10-hexahydro-9,10(1',2')-benzeno-1,4-methanoanthracene (HBMN)之合成 3.3.2 5‐butylbicyclo[2.2.1]hept‐2‐ene (NOHe)之合成 3.3.3 5‐(bromopropyl)bicyclo[2.2.1]hept‐2‐ene (NOBr)之合成 3.3.3.1 前驅物5-bromopentene 3.3.3.2 5‐(bromopropyl)bicyclo[2.2.1]hept‐2‐ene (NOBr) 3.3.4 [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro (phenylmethylene)bis(3-bromopyridine)ruthenium(II) (G3)之合成 3.4 聚降冰片烯之合成 3.5 聚降冰片烯之還原 3.6 交聯高分子薄膜之製備 第四章 結果與討論 4.1 單體的合成與標定 4.1.1 單體A (exo-1,4,4a,9,9a,10-hexahydro-9,10(1',2')-benzeno-1,4-methanoanthracene, HBMN)之製備與標定 4.1.2 單體B (5‐butylbicyclo[2.2.1]hept‐2‐ene, NOHe)之製備與標定 4.1.3 單體C (5‐(bromopropyl)bicyclo[2.2.1]hept‐2‐ene, NOBr)之製備與標定 4.2 高分子的合成與標定 4.3 還原高分子的合成與標定 4.4 離子交換容量、吸水率、溶脹率 4.5 熱性質 4.6 機械性質 4.7 形態學 4.8 離子傳導率 4.9 鹼性穩定性 第五章 結論 參考文獻

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