- 學位論文
有機溶劑可溶之聚苯胺及多孔性聚苯胺的合成與其結構、物性分析之研究
Studies on Synthesis, Structure and Properties of organic solvents-soluble polyanilines and porous polyanilines
摘要
摘 要 本論文以聚苯胺做進一步改質的方式，在聚苯胺主鏈上導入三種不同長短之雙端氯原子化合物：1,2-雙(2-氯乙氧基)乙烷、雙(2-氯乙基)醚及1,2-二氯乙烷，成功的合成出三種具氯端烷氧基側鏈之聚苯胺，稱之聚氮-氯端烷氧基苯胺（分別為ClEOEOE-NPAn、ClEOE-NPAn、ClE-NPAn），且藉由改變實驗條件，可合成出具交鏈結構之多孔性聚苯胺（EOEOE-PPAn、EOE-PPAn、E-PPAn）。 藉由溶解度測試，發現聚氮-氯端烷氧基苯胺皆可回溶於極性溶劑NMP及DMSO，ClEOEOE-NPAn在有機溶劑CHCl3 與THF良好的溶解性，且由UV-Vis 光譜分析證實為符合Beer's Law的真實溶液；由IR 及UV-Vis 光譜鑑定聚氮-氯端烷氧基苯胺為一具有氯端基側鏈結構之聚苯胺；由聚氮-氯端烷氧基苯胺之XRD圖譜，可知所導入之側鏈可誘導主鏈的規則排列，但由於鏈長的限制使得貢獻有限；而ClEOEOE-NPAn在DMSO、CHCl3及THF三種溶劑中皆可以DBSA有機酸作摻雜，摻雜後皆可全溶，經四探針法得知其未摻雜固態膜導電度為5.1´10-6 S/cm，經DBSA摻雜固態膜導電度為7.4´10-4 S/cm；由循環伏安計量分析（CV），發現三種聚氮-氯端烷氧基苯胺皆具電化學活性，與聚苯胺相比較：第一對氧化還原峰往較高電位偏移，第二對氧化還原峰往較低電位偏移，上述現象隨著導入的側鏈鏈長的增加而變得更明顯；在不同pH值電解質下的CV分析中，其第一對氧化還原反應過程中未涉及去質子和質子化的反應，而在pH值範圍-0.2~1.77之間，其第二對氧化還原反應為包含每失去一個電子伴隨失去二個質子之反應過程，文中也依此推導出其在pH值範圍 -0.2~1.77之下所對應之電化學氧化還原反應機構；由變電位UV-Vis光譜得知三種聚氮-氯端烷氧基苯胺皆具電變色行為，且與聚苯胺有相似的顏色變化。 經IR 光譜鑑定出多孔性聚苯胺為烷氧基在聚苯胺氮上取代之交鏈結構；由穿透式電子顯微鏡觀察其粒子大小約15-50 nm，為奈米級尺寸的聚苯胺顆粒；由表面積/孔隙度分析測定儀得知多孔性聚苯胺中EOEOE-PPAn具最大表面積（110.3 m2/g）及孔洞體積（0.25 cc/g），EOE-PPAn具最小孔徑（90.5 Å），且接入側鏈數隨導入鏈長長度而增加，可由熱重損失分析得到印證，文中也依此結果描繪多孔性聚苯胺的示意結構圖。
並列摘要
Abstract This thesis reports modifications of polyanilines by incorporation with three different chain lengths of chloride atoms at two end side compounds: [1,2-bis(2-chloroethoxy) ethane], [bis(2-chloroethyl) ether] and [1,2-dichloroethane]. Three kinds of N-chloro-alkoxylated polyanilines (ClEOEOE-NPAn, ClEOE-NPAn and ClE-NPAn) were successfully synthesized. We also synthesized three kinds of porous polyanilines (EOEOE-PPAn, EOE-PPAn and E-PPAn), which have chain-cross structures, with changing the experimental conditions. In solubility test, three N-chloro-alkoxylated polyanilines can well soluble in polar solvents (NMP and DMSO). ClEOEOE-NPAn can also have good solubility in organic solvents (CHCl3 and THF). They are proved as true solutions follow Beer's Law in UV-Vis spectra. We confirmed that N-chloro-alkoxylated polyanilines have chloro-alkoxyl side chain structures with IR and UV-Vis spectra. In XRD spectra, we find polyaniline's main chain can have regular arrangement by incorporation with side chain, but limitaion with chain length. ClEOEOE-NPAn can dope with dodecylbenzene sulfonic acid (DBSA) in three different solvents (DMSO, CHCl3 and THF), which have well-solubility after doped. With four probes method, the solid films conductivities of nutral ClEOEOE-NPAn and doped with DBSA are 5.1´10-6 S/cm and 7.4´10-4 S/cm, respectively. In cyclic voltammogram analysis (CV), we find three kinds of N-chloro-alkoxylated polyanilines all have electroactivity. Both N-chloro-alkoxylated polyanilines show a higher potential for the first redox process and a lower potential for the second redox process in comparison to polyaniline and this phenomenon become more obvious with the long chain length. In CV analysis with various pH values, the first redox reaction does not involve protonation or deprotonation. However, the second redox reaction involves two protons for each electron in the pH range -0.2 to 1.77. In UV-Vis spectra with different potential values, we find three kinds of N-chloro-alkoxylated polyanilines all have electrochromism and the same colours-changed phenomenon with polyaniline. Based on the above CV and UV-Vis results, we proposed a redox reaction mechanism of N-chloro-alkoxylated polyanilines. We prove the porous polyanilines are N-alkoxylated, which have chain-cross structures as analysed with IR spectra. The polymer particles sizes are about 15-50 nm with measured by transmission electron microscope (TEM). In pore surface area/pore size analysis (BET), we find EOEOE-PPAn have the biggest surface area (110.3 m2/g) and pore volume (0.25 cc/g) and EOE-PPAn have the smallest pore size (90.5 Å). The incorporation of the side chain numbers are increasing with the long chain length. This result is also confirmed from the thermogravimetric analysis (TGA). The porous polyanilines' molecular structures were proposed according to above results.