合成尾端官能基化導電高分子及利用偶合反應合成導電/絕緣之嵌段共聚高分子

Abstract

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.