具咪唑鹽之兩性離子交換膜的開發與製備

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蔣皓哲(Hao-Zhe Jiang) 查詢紙本館藏

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論文名稱

具咪唑鹽之兩性離子交換膜的開發與製備
(Development and preparation of amphoteric ion exchange membrane with imidazolium group)

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至系統瀏覽論文 (2025-7-23以後開放)

摘要(中)

本論文以開發含有親水端之聚合單體，用以製備兩系列具親水端之兩性離子高分子。
第一系列為兩性離子交換膜 PNB-CImS 的開發。首先製備出親水端單體 NB-CIm-4 與疏水端單體 NB-Hex，然後將兩者以不同比例進行 ROMP 聚合，製備出 PNB-CIm，之後將此高分子和 1,3-propansultone 反應，使其外接一個磺酸基團，得到一個同時具有正負電荷的高分子- PNB-CImS，當親水端比例為 50% 時，膜材的膨脹比及吸水率僅有 7.0% 和 8.9%，當親水端比例為 60% 時，目前導電度已達 0.019 S cm-1。
第二系列為兩性離子交換膜 PNB-BImS ，此系列為 PNB-CImS 系列的改良，經由上一個系列所得的成果，我們利用離子基團的數量、更密集的離子基團所成更大的離子通道而增加其導電度。成功合成新的親水端單體 Im-Cl 和 Im-ClS 用來和高分子 PNB-CIm 合成目標高分子 PNB-BImS ，並且在親水端比例為 40% 時可以順利成膜，導電度達 0.038 S cm-1 。

摘要(英)

In this study, two new series of hydrophilic monomers for preparation of amphoteric polymer for ion exchange membranes were developed.
The first series is the development of amphoteric ion exchange membrane PNB-CImS. First, monomer NB-CIm-4 and NB-Hex were prepared, and then the two monomers were subjected to ROMP polymerization in different mole ratios to prepare ionic PNB-CIm. The latter was treated with 1,3-propansultone to obtain a new ionic polymer, which with both positive and negative charges on the polymer. Membrane prepared by 50% hydrophilic ratio ionic polymer (PNB-CImS) exhibited 7.0% membrane swelling ratio and 8.9% water absorption ratio. Membrane prepared by 60% hydrophilic ratio ionic polymer (PNB-CImS) exhibited 0.031 S cm-1 ion conductivity.
The second series is the development of amphoteric ion exchange membrane PNB-BImS. This series is an improvement of the PNB-CImS series. As expect, we increase the number and density of ionic groups to increase its ion conductivity. The monomer Im-Cl and Im-ClS have been successfully synthesized to prepare PNB-BImS. Membrane prepared by 40% hydrophilic ratio ionic polymer (PNB-BImS) exhibited 0.038 S cm-1 ion conductivity.

關鍵字(中)

★ 離子交換膜

關鍵字(英)

論文目次

中文摘要 ................................ ................................ ................................ .. i
Abstract ................................ ................................ ................................ .. ii
謝誌 ................................ ................................ ................................ .. iii
重要名詞縮寫對照表重要名詞縮寫對照表重要名詞縮寫對照表重要名詞縮寫對照表 ................................ ................................ ............ ix
第一章緒論 ................................ ................................ ............................ 1
1-1 前言 ................................ ................................ ............................... 2
1-2 燃料電池簡介 ................................ ................................ ............... 4
1-3 燃料電池種類燃料電池種類燃料電池種類 ................................ ................................ ............... 9
1-3-1 質子交換膜燃料電池質子交換膜燃料電池質子交換膜燃料電池 (PEMFCs) ................................ 10
1-3-2 磷酸燃料電池磷酸燃料電池 (PAFCs) ................................ ................ 12
1-3-3 固態氧化物燃料電池固態氧化物燃料電池固態氧化物燃料電池 (SOFCs) ................................ ... 13
1-3-4 熔融碳酸鹽燃料電池鹽燃料電池 (MCFCs) ................................ .. 15
1-3-5 鹼性燃料電池鹼性燃料電池 (AFCs) ................................ .................. 16
1-3-6 固態鹼性燃料電池固態鹼性燃料電池固態鹼性燃料電池 (SAFCs) ................................ ....... 17
第二章文獻回顧 ................................ ................................ .................. 22
2-1 陰離子交換膜簡介 ................................ ................................ ..... 23
2-2 陰離子交換膜種類 ................................ ................................ ..... 24
2-3 陰離子交換基團的穩定性陰離子交換基團的穩定性陰離子交換基團的穩定性陰離子交換基團的穩定性 ................................ ......................... 40
2-4 陽離子交換膜簡介陽離子交換膜簡介陽離子交換膜簡介 ................................ ................................ ..... 46
2-5 陽離子交換膜種類陽離子交換膜種類陽離子交換膜種類 ................................ ................................ ..... 47
2-6 陽離子交換基團的穩定性陽離子交換基團的穩定性陽離子交換基團的穩定性陽離子交換基團的穩定性 ................................ ......................... 60
2-7雙極離子交換膜雙極離子交換膜 ................................ ................................ .......... 63
2-8 兩性離子交換膜兩性離子交換膜兩性離子交換膜 ................................ ................................ ......... 65
2-9 研究動機 ................................ ................................ ..................... 72
第三章實驗與儀器 ................................ ................................ .............. 77
3-1 實驗藥品 ................................ ................................ ..................... 78
3-1-1 實驗所使用之化學藥品實驗所使用之化學藥品實驗所使用之化學藥品 ................................ ................ 78
3-1-2 藥品的純化藥品的純化 ................................ ................................ .... 80
3-1-3 實驗所使用之溶劑實驗所使用之溶劑實驗所使用之溶劑 ................................ ........................ 81
3-1-4 溶劑除水 ................................ ................................ ........ 81
3-2 實驗儀器及技術原理實驗儀器及技術原理實驗儀器及技術原理 ................................ ................................ . 82
3-2-1 核磁共振光譜儀核磁共振光譜儀核磁共振光譜儀 (Nuclear Magnetic Resonance)； Bruker AVANCE 300 / 500MHz ................................ .... 82
3-2-2 熱重分析儀熱重分析儀 (Thermal Gravimetric Analysis, TGA)； Mettler Toledo TGA/SDTA 851 ................................ ..... 82
3-2-3 交流阻抗儀交流阻抗儀 (Alternating Current Impedance)；Autolab Pgstat 30 AUT system ................................ .................... 83
3-2-4 吸水膨潤比吸水膨潤比 (Water Uptake) 與尺寸變化率與尺寸變化率 (Swelling
Ratio) ................................ ................................ .............. 85
3-2-5 離子交換容量離子交換容量 (Ion Exchange Capacity, IEC) ............. 86
3-2-6 化學穩定性化學穩定性 (Chemical stability) ................................ .. 87
3-3 高分子合成後處理高分子合成後處理高分子合成後處理 ................................ ................................ ..... 87
3-3-1 高分子薄膜的製備高分子薄膜的製備高分子薄膜的製備 ................................ ........................ 87
3-3-2 高分子薄膜的鹼化高分子薄膜的鹼化高分子薄膜的鹼化 ................................ ........................ 88
3-3-3 高分子薄膜的酸化高分子薄膜的酸化高分子薄膜的酸化 ................................ ........................ 88
3-4 合成步驟 ................................ ................................ ..................... 85
3-4-1 6-bromo-1-hexene (1) 的合成 ................................ ....... 88
3-4-2 NB-Br-4 (2) 的合成 ................................ ....................... 89
3-4-3 NB-CIm-4 (3) 的合成 ................................ .................... 90
3-4-4 NB-Hex (4) 的合成 ................................ ....................... 91
3-4-5 NB- CImS (5) 的合成 ................................ ..................... 92
3-4-6 R-PNB-CIm-50、60、70 (6) 的合成 ........................... 93
3-4-7 R-PNB-CImS-50、60、70 (7) 的合成 .......................... 94
3-4-8 BIm-6 (8) 的合成 ................................ ........................... 95
3-4-9 NB-P (9) 的合成的合成 ................................ ............................ 96
3-4-10 Ims (10) 的合成的合成 ................................ ............................ 96
3-4-11 PNB-P-Im-50 (11) 的合成 ................................ ........... 97
3-4-12 Im-Cl (12) 的合成 ................................ ....................... 98
3-4-12 ImS-Cl (13) 的合成 ................................ ...................... 99
第四章結果與討論 ................................ ................................ ............ 101
4-1 PNB-CImS 系列之合成及討論系列之合成及討論系列之合成及討論 ................................ ................ 102
4-1-1 PNB-CIm-4 的 1H 核磁共振光譜結構探討核磁共振光譜結構探討核磁共振光譜結構探討核磁共振光譜結構探討 ............. 103
4-1-2熱穩定性 (Thermal Stability) ................................ ...... 105
4-1-3 離子交換容量離子交換容量 (Ion Conductivity) .............................. 106
4-1-4 吸水膨潤比吸水膨潤比 (W.U.) 與尺寸變化率與尺寸變化率與尺寸變化率 (S.R.) ............... 107
4-1-5 離子導電度離子導電度 (Ion Conductivity) ................................ .. 108
第五章結論 ................................ 111
參考文獻 ................................ .............................. 114
附錄 ................................ ................................ 121

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指導教授

陳銘洲

審核日期

2020-7-29

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