新型含多苯胺結構之芳香族高分子合成與電化學及電致變色特性之研究

Synthesis, Electrochemical and Electrochromic Properties of Novel Aromatic Polymers Containing Multi-Arylamine Moiety

黃莉婷(Li-Ting Huang)

指導教授 ： 劉貴生

國立臺灣大學/工學院/高分子科學與工程學研究所/碩士(2011年)

https://doi.org/10.6342/NTU.2011.10488

摘要

第一個4,4’-bis[(4-aminophenyl)amino]-diphenylamine單體化合物的合成，是由對氟硝基苯與4,4’-二氨基二苯胺進行親核性取代反應生成二硝基化合物，接著再用氫氣與鉑金屬催化還原而被合成出。另一個新型含三苯胺的二胺4,4’-bis[(4-aminophenyl)amino]-4”-methoxytriphenylamine首先合成 b4,4’-bis[(4-nitrophenyl)amino]-4”-methoxytriphenylamine由對氟硝基苯與4-甲氧基三苯胺進行親核性取代反應生成硝基化合物，接著再用氫氣與鉑金屬催化還原而被合成出。本論文分成四個章節，第一章為總體序論。第二章節包含了以4,4’-bis[(4-aminophenyl)amino]-diphenylamine、4,4’-bis[(4-aminophenyl)amino]-4”-methoxytriphenylamine和4,4’-bis[4-aminophenyl(4-methoxyphenyl)amino]-4”-methoxytriphenylamine為主體與不同的二酸酐利用一步或二步聚合法合成出三個系列新型含三苯胺或二苯胺取代衍生之陽極/陰極芳香族聚醯亞胺。第三章是以4,4’-bis[(4-aminophenyl)amino]-diphenylamine和4,4’-bis[(4-aminophenyl)amino]-4”-methoxytriphenylamine為主體與不同的醯氯合成出兩個系列新型含三苯胺或二苯胺取代衍生之芳香族聚醯胺。第四章節為結論。這五個系列新型三苯胺或二苯胺取代衍生之芳香族高分子之合成與基本特性、電化學及電致變色性質已被研究與比較。所有的高分子在極性非質子型溶劑中有好的溶解性，出色的薄膜成形能力，高的玻璃轉換溫度，好的熱穩定性和機械性質，較低的HOMO值。在利用電化學與光譜電化學的方法下，大部分的高分子也展現出色可逆的電致變色特性。然而，二苯胺取代的芳香族高分子(聚醯亞胺、聚醯胺)相較於三苯胺取代的芳香族高分子較無法有效的穩定經氧化後形成的陽離子自由基，是由於缺乏額外的苯環提供共振，且會釋出質子形成穩定的亞胺結構。因此，二苯胺取代的芳香族高分子較三苯胺取代的芳香族高分子具有較差的電化學穩定性，可歸因於胺基鏈段上釋出的質子無法從非酸性溶液中再獲得，意味著氧化態的亞胺結構無法回到原來的中性胺結構。

關鍵字

三苯胺 ； 二苯胺 ； 聚醯胺 ； 聚醯亞胺 ； 電致變色 ； 價間電子傳導

並列摘要

First compound, 4,4’-bis[(4-aminophenyl)amino]-diphenylamine was synthesized by hydrogen Pd/C-catalyzed reduction of the dinitro compound 4,4’-bis[(4-nitrophenyl)amino]-diphenylamine resulting from the triethylamine -mediated aromatic nucleophilic substitution reaction of 4,4'-diaminodiphenylamine with 4-fluoronitrobenzene. Another novel compound, 4,4’-bis[(4-aminophenyl)amino]-4”-methoxytriphenylamine was synthesized by hydrogen Pd/C-catalyzed reduction of the dinitro compound 4,4’-bis[(4-nitrophenyl)amino]-4”-methoxytriphenylamine resulting from the triethylamine-mediated aromatic nucleophilic substitution reaction of 4,4’-diamino-4’’-methoxytriphenylamine with 4-fluoronitrobenzene. This study has been separated into four chapters. Chapter 1 is general introduction. Chapter 2 includes three series of novel ambipolar aromatic polyimides based on 4,4’-bis[(4-aminophenyl)amino]-diphenylamine, 4,4’-bis[(4-aminophenyl)amino]- 4”-methoxytriphenylamine and 4,4’-bis[4-aminophenyl(4-methoxyphenyl)amino]- 4”-methoxytriphenylamine, and various tetracarboxylic dianhydrides via one-step and conventional two-step polymerization. The chapter 3 include two series of novel aromatic polyamides and derived from 4,4’-bis[(4-aminophenyl)amino]-diphenylamine, and 4,4’-bis[(4-aminophenyl)- amino]-4”-methoxytriphenylamine, and various diacid chlorides by low temperature polycondensation. Chapter 4 is conclusions. The synthesis, basic characterization, electrochemical and electrochromic properties of five series of novel aromatic triphenylamine (TPA) or diphenylamine (DPA)-substituted derived polymers were investigated and compared. All polymers had good solubility in many polar aprotic solvents, and exhibited excellent thin-film-forming ability. In addition to high Tg values, good thermal stability, mechanical properties, and lower HOMO energy levels, most of the obtained polymers also revealed excellent reversibility of electrochromic characteristics by the electrochemical and spectroelectrochemical methods. However, the DPA-based polymers could not effectively stabilize the cationic radicals of oxidized form comparing to the corresponding TPA-based polymers due to lack of extra phenyl rings for resonance and the subsequent removing protons to form the stable imine structure. Thus, the electrochemical behavior of lower electrochemical stability of DPA-based polymers than the corresponding TPA-based polymers might be attributed to the protons of amino linkages after removal could not be regained in the non-acidic solution, meaning the oxidized imine group could not go back to the original neutral amine state.

並列關鍵字

triphenylamine ； diphenylamine ； polyamide ； polyimide ； electrochromism ； intervalence-charge transfer (IV-CT)

參考文獻

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