戴子安臺灣大學：化學工程學研究所鍾惠怡Chung, Hui-YiHui-YiChung2007-11-262018-06-282007-11-262018-06-282006http://ntur.lib.ntu.edu.tw//handle/246246/52386硬桿-柔曲嵌段式共聚物(Rod-coil block copolymer)所產生的微相分離（microphase separation）結構是近年熱門的研究領域，本研究中，先以Siegrist polycondensation合成尾端具有醛基的導電高分子(rodlike) DEHPPV，因為單體電子效應影響，可得到Mn約7000，分子量分佈(PDI)小的DEHPPV，再將DEHPPV尾端的imino group酸化為醛基(aldehyde)。 將尾端具有醛基的DEHPPV與P2VP(及PtBOS)陰離子進行偶合(coupling)反應合成出嵌段式共聚物DEHPPV-P2VP及DEHPPV-PtBOS。嵌段式共聚物以膠體滲透層析(GPC)測得DEHPPV-P2VP Mn約12000，PDI 1.3；DEHPPV-PtBOS Mn約14000，PDI 1.4，在紫外-可見光光譜(UV-vis)及螢光光譜(PL)部分，相較於純DEHPPV及混摻（blend）系統，嵌段式共聚物因為含有P2VP(及PtBOS)鏈段，使得共軛長度產生變化而有藍移現象。由TEM發現DEHPPV-P2VP有纖維狀結構。The self-assembly behavior of block copolymers have attracted widespread interest in both fundamental and technological contexts. There is an even greater interest in conducting/insulating block copolymers for use in organic electronics, e.g. solar cell, light emitting diode etc. The objective of this thesis is to develop methods to synthesis conducting polymers with well-defined structure and molecular weight as well as to develop methods to synthesize the conducting/insulating block copolymers. This thesis is divided into two parts. In the first part of the thesis, soluble and monodispersed conducting polymers of poly(2,5-di(2'-ethylhexyloxy)-1,4- phenylenevinylene) (DEH-PPV) with an aldehyde group at each chain end were successfully synthesized by the Seigrist polycondensation of 2,5-di(2-ethylhexyloxy) -4-methyl-N- benzylideneaniline monomer. The optical and thermal properties of the PPV are examined. In the second part of the thesis, a method to synthesize DEH-PPV-block-poly (2-vinyl pyridiene) (PPV-P2VP) and DEH-PPV-block-poly (t-butoxy styrene) (PPV-PtBOS) were developed by using condensation reaction of anionically polymerized living P2VPLi and PtBOSLi, respectively with the aldehyde terminated PPV. Transmission electron microscopy of the copolymers shows self-assembled nanostructure with a length scale in the range of 10-20nm.致謝 I 摘要 II 目錄 IV 圖目錄 VIII 第一章 緒論 1 第二章 文獻回顧 5 2.1 陰離子聚合 5 2.2.1 陰離子聚合之單體 5 2.1.2 陰離子聚合之起始劑 6 2.1.3 陰離子聚合之起始反應 7 2.1.4 陰離子聚合之成長反應 7 2.1.5 陰離子聚合之終止反應 8 2.2 Poly ( p-phenylenevinylene)s (PPVs)的合成方法 9 2.2.1 Precursor route（Gilch、Wessling and Zimmerman等） 9 2.2.2 Heck coupling 10 2.2.3 Wittig (-Horner) condensation 11 2.2.4 Stepwise Routes 13 2.2.5 Siegrist Polycondensation 16 2.3 Oligo(phenylenevinylene)s之光學性質 19 2.4 Block copolymer自組裝特性 21 2.5 含PPV之嵌段式共聚物之合成與性質 22 第三章 實驗 28 3.1 實驗藥品 28 3.2 實驗儀器 29 3.3 實驗步驟 30 3.3.1 DEHPPV單體合成 30 3.3.2 陰離子聚合 39 3.3.3 嵌段式共聚物 DEHPPV-b-P2VP 及 DEHPPV-b-PtBOS 44 第四章 結果與討論 45 4.1 DEHPPV及其單體合成與鑑定 45 4.1.1 2,5-Di(2’-ethylhexyloxy)toluene 46 4.1.2 2,5-Di(2’-ethylhexyloxy)-4-methylbenzaldehyde 47 4.1.3 2,5-Di(2”-ethylhexyloxy)-4’-methyl-N-benzylideneaniline 49 4.1 4 DEHPPV合成鑑定 51 4.2 DEHPPV DSC熱分析 54 4.3 DEHPPV-P2VP 嵌段式共聚物之合成 55 4.4 DEHPPV-PtBOS共聚物之合成 59 4.5 DEHPPV-P2VP 與DEHPPV-PtBOS 嵌段式共聚物之UV-vis與PL 62 4.6 DEHPPV-P2VP之TEM 65 參考文獻 692178561 bytesapplication/pdfen-US嵌段式共聚物尾端官能基化聚(對亞苯基-亞乙烯基)偶合反應Block copolymerEnd-functionalized. PPVCoupling reactionthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/52386/1/ntu-95-R93524017-1.pdf