具C2-咪唑鹽之高親水端陰離子交換膜的開發

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题名:	具C2-咪唑鹽之高親水端陰離子交換膜的開發
作者:	鄒昀;Tsou,Yun
贡献者:	化學學系
关键词:	燃料電池;陰離子交換膜;高分子化學;有機合成;fuel cell;anion exchange membrane;polymer chemistry;organic chemistry
日期:	2016-07-25
上传时间:	2016-10-13 12:43:25 (UTC+8)
出版者:	國立中央大學
摘要:	本論文利用新開發的-長碳鏈C2-咪唑鹽離子交換集團開發出兩系列之陰離子交換膜材料。以高化學穩定性之C2-咪唑鹽取代傳統N1-咪唑鹽，進行材料之合成。第一系列以poly(ether ether ketone) (PEEK) 為主幹，第二系列以polystyrene (PS) 為主幹，分別將其接上高比例之C2-咪唑鹽離子親水端，除期藉由長碳鏈之引入改良高分子膜材之柔軟性之外，亦期望以此長碳鏈區隔高分子主幹及親水端官能基，增其親水端之聚集(有較合適的相分離)以提升膜材之離子導電度。第一系列材料以PEEK為高分子主幹，接上高比例之長碳鏈C2-咪唑鹽離子交換集團，並藉由改變分子設計以調控其分子內離子交換集團含量，進而改變其IEC值及離子導電度，以合成出兩個具不同比例親水端的高分子材料: PEEK-CIM 以及 PEEK-DCIM。此系列膜材具有十分良好的尺寸穩定性及熱穩定性，目前離子導電度最高可達 0.017 S/cm 。第二系列材料，以 polystyrene (PS) 為高分子主幹，接上高比例之長碳鏈C2-咪唑鹽離子交換集團，開發出一系列新的膜材: PS-c-CIM。並且在合成時適量添加交聯劑，能夠改善薄膜之機械強度和有效抑制尺寸變化率。並藉由調控交聯劑之比例，製作出一系列的高分子材料。完成合成並純化後，我們將材料送往合作夥伴工研院進行後續之加工成膜，並進行性質量測。 ;In this study, two series of anion exchange membranes were developed based on the new developed hydrophilic 2-(5-bromopentyl)-1,3-dimethyl-imidazolium iodide(C-IM+ I-). In frist series, poly(ether ether ketone) (PEEK)-CIM was developed via alkylation reaction of C-IM+ I- with PEEK bearing OH groups (PEEK-OH). The later was prepared via condensation polymerization of 2-methoxyhydroquinone and 4,4′-difluorobenzophenone, which was then underwent methyl deprotection to give the corrpesonding PEEK-OH. Highly hydrophilic PEEK-CIM exhibits good ionic conductivity of 0.017 S/cm at room temperature. To further enhance the conductivity of this series, new diol monomer, 4,4′-(propane-2,2-diyl)bis(2-methoxyphenol)(BPDOH), was prepared, which was then polymerized with 4,4′-difluorobenzophenone to give the new PEEK-DCIM. With higher hydrophilic portion, the later exhibits higher ion exchange capacity (IEC) and ionic conductivity. In the second series, polystyrene based-CIM polymer was prepared via alkylation of polystyrene-OH with hydrophilic C-IM+ X-. Since highly ionic PS-CIM couldn’t be used for membrane preparation, appropriate amount (from 1% to 10%) of dihalide was added as crosslinker during PS-OH alkylation to give the corresponding crosslinked PS-c-CIM-(1%-10%). Membrane prepared from PS-c-CIM-(5%) by ITRI exhibits IEC of 1.X (mmole/g), swelling ratio of 15%, and the highest ionic conductivity up to 0.07 S/cm.
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