新型含三苯胺基團之共軛高分子材料: 合成、理論計算、光電特性及電致變色性質研究

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研究生：	吳翰宇 Han-Yu Wu
論文名稱：	新型含三苯胺基團之共軛高分子材料: 合成、理論計算、光電特性及電致變色性質研究 New Conjugated Polymer Materials Containing Triphenylamine: Synthesis, Theoratical , Optical, Electrochemical and Electrochromic Properties
指導教授：	廖德章 Der-jang Liaw
口試委員:	汪昆立 Kun-li Wang 洪伯達 Po-da Hong
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2010
畢業學年度：	98
語文別：	英文
論文頁數：	67
中文關鍵詞：	共軛高分子、三苯胺、電致變色
外文關鍵詞：	conjugated polymer, triphenylamine, electrochromic
相關次數：	點閱：309 下載：4
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上一筆

第一章關於一新型之雙溴化物與芴之硼酸藉鈴木偶合反應具合而成一新型之高分子材料。其玻璃轉移溫度達140 oC，Td10達458 oC。此高分子材料薄膜塗於ITO玻璃上藉循環伏安儀測試顯示出兩對可逆之氧化還原峰於0.7伏特及1.0伏特。並於0伏特至1.3伏特具從淺綠至深綠再至深藍之電致變色行為。其在860nm之著色與褪色秒數分別為4.25秒及7.22秒; 於560nm之著色與褪色秒數分別為5.51秒及6.48秒。
第二章關於一新型具快速應答時間、低電壓且具近紅外光之電致變色功能之含三苯胺共軛高分子（ＰＢＴＰＡＦＬ）。其於紫外光－可視光－近紅外光之吸收波長變化均為可逆且具明顯之由淺綠至深綠再至普魯士藍的顏色變化，且其具有快速之著色速度2.58秒及退色速度1.76秒。與其他材料P1及P2之比較可得，導入越具推電子之官能基於三苯胺之對位苯環位置，越能降低氧化電位及避免電化學偶合反應。此材料具高分子量及高溶解度，以及高耐熱(Td10 超過450 oC)。同時，結合理論化學計算，也將提出新的分子軌域理論之氧化還原機制。

A novel dibromo compound containing unsymmetrical substituted bi-triarylamine was synthesized. A conjugated polymer was prepared via the Suzuki coupling from the newly prepared dibromo compound and 9,9-dioctylfluorene-2,7-bis (trimethyleneboronate). The glass transition temperature (Tg) of the conjugated polymer was 140 oC, 10% weight-loss temperatures (Td10) in nitrogen was 458 oC, and char yield at 800 oC in nitrogen higher than 64%. Cyclic voltammogram of the polymer film cast onto an indium-tin oxide (ITO)-coated glass substrate exhibited two reversible oxidation redox couples at 0.70 and 1.10 V v.s. Ag/Ag+ in acetonitrile solution. The polymer films revealed excellent stability of electrochromic characteristics, with a color change from yellow green of the neutral form to the dark green and blue of oxidized forms at applied potentials ranging from 0 to 1.3 V. The color switching time and bleaching time were 4.25 s and 7.22 s for 860 nm, and 5.51 s and 6.48 s for 560 nm.
A new rapid switching near-IR electrochromic conjugated propeller-shape polymer (PBTPAFL) with lower oxidation potential containing di-triarylamine group was synthesized via Suzuki coupling approach. The observed UV-vis-NIR absorption change in the PBTPAFL film at various potentials are fully reversible associated with strong color changes from original light green to dark green and then to a Prussian blue. Excellent continuous cyclic stability of electrochromic characteristic with rapid color switching time 2.58s and bleaching time 1.76s was found as well. Compared with P1 and P2, the introduction of more electron-donating propyl phenyl group in the para position of PBTPAFL lowered the oxidative potential and prevented coupling reaction during the electrochromic procedure. The high molecular weight conjugated polymer having high thermal stability with Td10 more than 450 oC has excellent solubility in common organic solvents such as NMP, THF, chloroform, toluene, xylene, and benzene at room temperature (25 oC) due to the propeller-shape structure and long alkyl chain on fluorene. Herein, from the combination of the experimental and computational study, we proposed a mechanism based on molecular orbital theory to explain the electrochromic oxidation behavior.

目     錄

中文摘要		3
英文摘要		4
誌　　謝		5


Chapter I:
An Electrochromic Material Containing Unsymmetrical Substituted N,N,N’N’-Tetraaryl-1,4-phenylenediamine : Synthesis and their Optical, Electrochemical and Electrochromic Properties

Introduction	9
1.	Materials		10
2. Measurements	10
3	Synthesis of monomers	11
4  Synthesis of polymer	14
5  Synthesis of model compounds	15
Results and Discussion
1 Synthesis and Characterization.	16
2 Basic properties	23
3 Optical Properties.	23
4 Electrochemical Properties.	26
5 Electrochromic Characteristics	29
Conclusions	  31
References and notes	32


Chapter II
A New Rapid Switching Electrochromic Conjugated Polymer with Lower Oxidative Potential : Synthesis, Electrochemical and Theoretical Investigation

Introduction	37
1.	Materials		39
2. Measurements	39
3	Synthesis of monomers	40
4  Synthesis of polymer	43
5  Synthesis of model compounds	44
Results and Discussion
1 Synthesis and Characterization.	45
2 Thermal properties	51
3 Optical Properties.	52
4 Electrochemical Properties.	54
5 Theoretical study for oxidation mechanism	56
6 Electrochromic Characteristics	60
Conclusions	  62
References and notes	63

                                

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全文公開日期 2015/02/03 (校內網路)
全文公開日期本全文未授權公開 (校外網路)
全文公開日期 2015/02/03 (國家圖書館：臺灣博碩士論文系統)

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