含二苯並呫噸結構之聚芴高分子合成與其性質之研究

Synthesis and Properties of Novel Polyfluorenes Containing Dibenzoxanthene Moieties

丁德依(De-I Ting)

指導教授 ： 汪昆立

國立臺北科技大學/工程學院/化學工程研究所/碩士(2013年)

https://doi.org/10.6841/NTUT.2013.00703

摘要

聚芴（Polyfluorene）本質上是一高電洞移動率之傳導材料，一般藉由導入多電子與缺電子基團改善電子及電洞傳導性。
　　本實驗成功合成五種含有二苯並呫噸的聚芴高分子，先合成出新型雙溴單體4-(3,11-dibromo-14H-dibenzo[a,j]xanthen-14-yl)aniline和帶有三苯胺官能基的4-(3,11-dibromo-14H-dibenzo[a,j]xanthen-14-yl)-N,N-bis(4-nitrophenyl)aniline，分別與具有雙硼酸環官能基之fluorene聚合成出PFDBX和PFTAN，兩種聚芴高分子。之後以PFDBX高分子進行側鏈基取代反應合成出PFDMe、PFDAr和PFDArMe三種新型高分子，以NMR與FT-IR鑑定結構，並探討其熱性質、光電性以及溶解性。
　　合成之高分子在260~400nm之間具有強烈UV-Vis吸收，最大放光波長範圍約在400~459nm之間。這些聚芴高分子的玻璃轉移溫度在149~169℃之間，氮氣下的5%和10%重量損失分別在364~410℃和417~433℃之間。側鏈改質後高分子循環伏安圖（CV）皆顯示出兩個還原峰且不具可逆性。

關鍵字

二苯並呫噸 ； 聚芴 ； 三苯胺 ； 呫噸

並列摘要

Polyfluorene is a well-known hole-transporting material with high mobility. Attempts have been made to improve the electron and hole-transporting properties of polyfluorenes by introducing electron-donor and electron-acceptor moieties, respectively.
　　Five novel polyfluorenes containing dibenzoxanthene moieties were successfully synthesized. First, 4-(3,11-dibromo-14H-dibenzo[a,j]xanthen-14-yl) aniline and 4-(3,11-dibromo-14H-dibenzo[a,j]xanthen-14-yl)-N,N-bis(4-nitrophenyl) aniline were prepared and polymerized with 2,2'-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(1,3,2- dioxaborolane) to form two fluorene-based copolymers coded as PFDBX and PFTAN . Then the amino groups of the PFDBX were modified on the side chain with acyl chloride compounds to from three new polyfluorenes coded as PFDMe , PFDAr and PFDArMe.
　　The structures of polyfluorenes were confirmed by FT-IR and NMR. The thermal properties, optical properties and solubility of the polyfluorenes were investigated and discussed. The polyfluorenes exhibited UV-Vis absorption band at 260~400 nm and showed maxima potoluminescence emission at 400~459 nm. These polyfluorenes showed glass transition temperatures from 149 ℃ to 169℃, and they showed 5% and 10% weight-loss temperatures from 364℃ to 410℃ and from 417℃ to 433℃, respectively. Cyclic voltammetry curves of the polyfluoenes showed two irreversible reduction peaks.

並列關鍵字

dibenzoxanthene ； polyfluorene ； triphenylamine ； xanthene

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