研究生: |
劉彥群 Yen-Chun Liu |
---|---|
論文名稱: |
高性能高分子之合成及其性質探討 Synthesis and Characterization of High Performance Polymer |
指導教授: |
陳志堅
Jyh-Chien Chen, |
口試委員: |
李宗銘
none 王英靖 none 陳耿明 none 陳建光 Jem-Kun Chen 游進陽 Chin-Yang Yu |
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: | 2012 |
畢業學年度: | 101 |
語文別: | 中文 |
論文頁數: | 142 |
中文關鍵詞: | 聚甲亞胺 、水解現象 、後聚合現象 、聚并咪唑 、醯化反應 、質子傳導率 |
外文關鍵詞: | polyazomethines, hydrolysis, post-polymerization, polybenzimidazoles, acylation reaction, proton conductivity |
相關次數: | 點閱:241 下載:5 |
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本研究分為兩大部分,第一部分為含非共平面聯苯結構之芳香族聚甲亞胺的合成、性質與水解現象。第二部分為含有2,2’-disubstituted-4,4’-diphenylether結構之新型聚并咪唑之合成、性質及其質子交換膜燃料電池應用。
第一部分中,含有拉電子三氟甲基與非共平面聯苯結構之新型聚甲亞胺已成功的以室溫減壓的方法進行聚合。在本研究中發現聚甲亞胺在溫度高於50 oC的DMSO溶液中會發生水解的現象。水解現象來自於甲亞胺基團的裂解,此現象隨著溫度升高越發顯著。當固態聚甲亞胺膜在減壓(0.27 torr)的狀況下加熱至200 oC後聚合現象即會發生。新型聚甲亞胺的HOMO以及LUMO能階皆小於一般的聚甲亞胺。本研究中所合成之新型聚甲亞胺含有拉電子三氟甲基與非共平面聯苯結構,同時結合了極佳的溶解度與優良的熱穩定,相信可將其應用於設計新型共軛高分子之電子受體結構。
第二部分中,在2及2’位置含有苯環的4,4’-二苯醚結構之新型四胺已被成功的開發。以此新型四胺與不同的二酸進行進行聚并咪唑的聚合皆會發生醯化(acylation)反應。此競爭反應導致無法合成線性以及高分子量的聚并咪唑。以含有溴基側基的新型4,4’-二苯醚二酸所合成的PBI-7擁有極佳的溶解度與熱穩定性。PBI-7質子交換膜是以有機溶劑法製成,磷酸摻雜後得到其ADL為6.9,含磷酸重量百分比為221%。PBI-7進行半電池量測在80 oC的質子傳導率為9.0 × 10-3 (S/cm),160 oC的質子傳導率為2.6 × 10-2 (S/cm),質子傳導活化能為21.12 (kJ/mol)。根據半電池數據顯示,新型聚并咪唑PBI-7將可成功的應用在質子交換膜燃料電池。
This dissertation includes two parts. First part is “Synthesis, Characterization and Hydrolysis of Aromatic Polyazomethines Containing Non-Coplanar Biphenyl Structures”. Second part is “Synthesis, Characterization and Proton Exchange Membrane Fuel Cell Applications of Novel Polybenzimidazole Containing 2,2’-Disubstituted-4,4’-diphenylether Moiety”.
In the first part, new polyazomethines containing electron-withdrawing trifluoromethyl group and non-coplanar biphenyl structures were prepared at room temperature under reduced pressure. It was found that these polyazomethines would undergo hydrolysis in DMSO solution at temperature higher than 50 oC. The hydrolysis, evidenced by 1H NMR spectra and GPC chromatograms, was resulted from the reverse reaction of azomethine formation and was facilitated at higher temperature. The GPC results also suggested that post-polymerization would be possible if polyazomethine films were heated at elevated temperature (200 oC) under reduced pressure (0.27 torr). The HOMO (-5.69 to -5.96 eV) and LUMO (-3.04 to -3.18 eV) energy levels of the new polyazomethines are much lower than those of other polyazomethines. Combined with the excellent solubility and good thermal stability, non-coplanar biphenyl structure containing electron-withdrawing trifluoromethyl group could be a new candidate as electron acceptor for the structure design of new conjugated polymers.
In the second part, A novel tetraamine containing 4,4’-diphenylether moiety and phenyl ring as side group was prepared via eight steps from 4,4’-oxydianiline (4,4’-ODA). It was found that side acylation reaction of polybenzimidazole would take place during polycondensation under appropriate conditions. The novel tetraamine which had phenyl ring at 2 and 2’ positions provides more opportunities for side acylation reaction. According to the competition of side acylation reaction and linear polymerization, high-molecule weight polybenzimidazole could not be obtained when this novel tetraamine was used. PBI-7 was synthesized from commercial 3,3’-diaminobenzidine and novel diacid which had 4,4’-diphenylether moiety and bromine group at 2 and 2’ position. It exhibited excellent solubility in common organic solvents and good thermal stability. The decomposition temperature at 5% weight loss under nitrogen was 439oC。The proton exchange memebrane of PBI-7 was prepared in 3% (by weight) NMP solution. The phosphoric acid doping level is 6.9 and phosphoric acid doped weight percent is 221% at room temperature. The proton conductivity of PBI-7 is 9.0 × 10-3 (S/cm) at 80 oC and 2.6 × 10-2 (S/cm) at 160 oC. The activation energy of proton conductivity which was calculated from Arrhenius equation is 21.12 (kJ/mol). Combined with the excellent solubility, good thermal stability and proton conductivity, PBI-7 containing 4,4’-diphenylether moiety and bromine group at 2 and 2’ position could be a new material as proton exchange membrane for fuel cell applications.
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