戴子安臺灣大學：高分子科學與工程學研究所陳孟輝Chen, Meng-HuiMeng-HuiChen2007-11-292018-06-292007-11-292018-06-292005http://ntur.lib.ntu.edu.tw//handle/246246/62897在本研究中，我們討論如何合成一硬桿-柔曲之團鏈共聚高分子，其中硬桿鏈段為聚三己烷基噻吩（P3HT），柔曲鏈段為聚二乙烯吡啶（P2VP）。為了達到這個研究目的，我們先利用格林納置換法合成導電高分子P3HT，並將其尾端乙烯化，在經核磁共振儀確定結構後，利用此尾端乙烯化之P3HT與P2VP陰離子反應進行接合。 合成之團鏈共聚高分子在純化後分別利用凝膠滲透層析儀、紫外-可見光吸收光譜儀、核磁共振儀、質譜儀，以及熱性質分析（熱重損失分析儀、微差掃描熱卡計），分析其化學及物理性質，並利用以推算P3HT的分子量，確定其分子量比例P2VP比上P3HT為5比3。接著利用穿透式電子顯微鏡觀察此團鏈共聚高分子自我排組之情形，可發現形成球狀微結構。 此外，我們更進一步合成尾端醛基化之P3HT，比較其與P2VP陰離子之反應性，是否較尾端乙烯化之P3HT為佳。 另外，我們合成磺酸化聚噻吩，觀察其自我添補之效應對吸收光譜之影響。This thesis describes a way to synthesize rod-coil block copolymers consisting of Poly(3-Hexylthiophene) (P3HT) as rigid rod and Poly(2-Vinylpyridine) (P2VP) as flexible coil. In this study, we first synthesize a conducting polymer, P3HT, via Grignard metathesis method. And we functionalize the polymer chain end of P3HT into vinyl group. After characterize from 1H NMR spectroscopy, we use the end functionalized P3HT to proceed coupling reaction with P2VP anion. The block copolymer is fully characterized with Gel permeation chromatography, UV-vis, PL, 1H NMR, MALDI-TOF-MS, TGA, DSC. From the results from spectroscopy we estimate the ratio of P2VP to P3HT is 5:3. And, images from transmission electron microscopy show that block copolymer is self-assembled into spherical structure. Furthermore, we synthesis aldehyde terminated P3HT for the purpose to see if it exhibits better reactivity with P2VP anion than vinyl terminated P3HT. Also, we synthesis sulfonated polythiophene, and observe the effect of self-doping on UV-vis spectrum.摘要..........................................................................................................Ⅰ Abstract.....................................................................................................Ⅱ 目錄..........................................................................................................Ⅲ 圖索引......................................................................................................Ⅶ 第一章 緒論..............................................................................................1 第二章 文獻回顧......................................................................................3 2-1 陰離子聚合............................................................3 2-1-1 陰離子反應之單體.......................................................3 2-1-2 陰離子反應之起始劑...................................................4 2-1-3 陰離子反應之起始反應...............................................5 2-1-4 陰離子反應之成長反應...............................................5 2-2 團鏈共聚高分子（Block Copolymer）...................................6 2-3 聚三烷基噻吩（P3AT）..........................................................8 2-3-1 P3AT之合成方法演進...................................................8 2-3-2 P3AT側鏈對排列的影響............................................10 2-3-3 P3AT分子量之研究....................................................11 2-3-4 P3AT的光電性質探討................................................12 2-3-5 P3AT的應用................................................................12 2-4 合成尾端官能基化之P3AT................................................13 2-5 利用尾端官能基化之高分子合成block copolymer...........14 2-6 合成側鏈官能基化之Poly(thiophene)................................15 第三章 實驗方法....................................................................................16 3-1 實驗步驟..............................................................................16 3-1-1 陰離子聚合.................................................................16 3-1-1-1 單體純化..........................................................16 3-1-1-2 溶劑純化..........................................................17 3-1-1-3 陰離子聚合......................................................18 3-1-2 Poly(3-Hexylthiophene) （P3HT）合成........................20 3-1-2-1 3-Hexylthiophene合成.......................................20 3-1-2-2 2,5 Dibromo 3-Hexylthiophene合成.................21 3-1-2-3 P3HT的聚合......................................................21 3-1-3 尾端乙烯化之P3HT聚合............................................22 3-1-4 尾端醛基化之P3HT聚合............................................23 3-1-5 利用尾端乙烯化之P3HT與P2VP陰離子進行接合...24 3-1-6 利用尾端醛基化之P3HT與P2VP陰離子進行接合...25 3-1-7 利用溶解度不同純化block copolymer.......................25 3-1-8 利用尾端醛基化之P3HT與PEO進行接合………....26 3-1-9 側鏈磺酸化之Poly(thiophene)合成............................27 3-2 實驗儀器..............................................................................29 3-3 實驗藥品..............................................................................30 第四章 結果與討論................................................................................31 4-1 陰離子聚合P2VP.................................................................31 4-2 尾端乙烯化P3HT合成鑑定部份........................................32 4-2-1 3-Hexylthiophene之合成鑑定......................................32 4-2-2 2,5-Dibromo-3-Hexylthiophene之合成鑑定................33 4-2-3 尾端乙烯化P3HT之合成與分析................................35 4-2-3-1 尾端乙烯化P3HT反應機制探討.....................35 4-2-3-2 尾端乙烯化P3HT之分子量鑑定與分析.........40 4-2-3-3 尾端乙烯化P3HT之尾端基分析.....................41 4-3 以尾端乙烯化P3HT合成block copolymer與鑑定...........42 4-3-1 P3HT與陰離子反應機制............................................42 4-3-2 尾端乙烯化P3HT與P2VP陰離子反應機制...............43 4-3-3 乙烯化P3HT與P2VP陰離子反應GPC結果...............43 4-3-4 Copolymer 1光學性質檢定.........................................45 4-3-5 Copolymer 1 1H NMR圖譜分析..................................50 4-3-6 Copolymer 1 TGA熱分析..........................................52 4-3-7 Copolymer 1 DSC熱分析.............................................53 4-3-8 Copolymer 1 TEM圖譜..............................................54 4-3-9 Copolymer 1 各結果綜合討論...................................55 4-4 尾端醛基化P3HT之合成與分析........................................58 4-5 以尾端醛基化P3HT與P2VP合成block copolymer............61 4-6 以尾端醛基化P3HT與PEO合成block copolymer..............62 4-7 合成側鏈磺酸化之Poly(thiophene)....................................63 第五章 結論............................................................................................68 第六章 參考文獻....................................................................................70 第七章 附錄............................................................................................73 7-1 利用尾端乙烯化P3HT合成Copolymer之附圖..................73 7-2 合成尾端醛基化之P2VP.....................................................751830527 bytesapplication/pdfen-US團鏈共聚高分子聚三己烷基噻吩導電高分子尾端官能基化聚二乙烯吡啶微相分離磺酸化聚噻吩自我添補block copolymerPoly(3-Hexylthiophene)conducting polymerend functionalizedPoly(2-Vinylpyridine)micro-phase separationsulfonated polythiopheneself-dopingthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/62897/1/ntu-94-R92549017-1.pdf