含三苯胺及1,3,4-噁二唑結構之聚芳香醚合成與其性質研究

Synthesis and Properties of Poly(aryl ether)s Containing Triphenylamine and 1,3,4-Oxadiazole Moieties

10.6841/NTUT.2013.00717

莊昭宇

聚芳香醚 ； 三苯胺 ； 1,3,4-噁二唑 ； 親核取代 ； poly(aryl ether)s ； triphenylamine ； 1,3,4-oxadiazole ； nucleophilic displacement

臺北科技大學化學工程研究所學位論文

2013年

碩士

汪昆立

繁體中文

本實驗合成3種含三苯胺及1,3,4-噁二唑之雙氟單體，再分別與不同的雙酚進行親核取代聚合反應，形成主鏈含有芳香醚之新型高分子，並依芳香醚主鏈位置不同，來探討其熱性質、光學性質、電化學性質及應用。 單體與高分子皆以傅立葉轉換紅外線光譜儀 ( FT-IR )、核磁共振儀( NMR ) 鑑定其結構。在溶解度測定方面，這些高分子皆能溶於有機極性溶劑如NMP、DMF、DMSO、DMAc、THF、DCM中。光學性質方面，在NMP溶液中，UV-vis 最大吸收峰約位於280 nm和360 nm，PL放射峰則是在458 nm ~ 507 nm；而熱性質方面，玻璃轉移溫度介於163 ~ 219°C之間，在氮氣下5%及10%重量損失溫度為358 ~ 465°C及392 ~ 486°C；固有黏度為0.10 ~ 1.26 dL/g；其電化學性質是由循環伏安法 ( CV ) 所檢測，聚芳香醚高分子的HOMO和LUMO值可藉由氧化電位和吸收光譜的起始波長計算而得，分別是-5.54 ~ -5.42 eV 和-2.52 ~ -2.25 eV 。

We synthesized three types of difluoro monomers containing triphenylamine and 1,3,4-oxadiazole. The monomers were polymerized with different bisphenols respectively to form novel poly( aryl ether )s by the nucleophilic displacement. According to the position of the fluoro atoms in the polymers, the thermal properties, optical properties and electrochemical properties of the polymers were investigated and discussed. The structures of monomers and polymers were confirmed by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy. The polymers showed excellent solubility in organic polar solvents such as NMP, DMF, DMSO, THF, and DCM. The polymers exhibited UV-vis maximum absorption bands about 280nm and 360nm, and showed PL maximum emission peaks at 458nm to 507nm in NMP solution. The glass transition temperatures ranged from 163 to 219°C, the temperature at 5% and 10% weight loss measured by TGA were in the range of 358 to 465°C and 392 to 486°C under nitrogen, respectively. The inherent viscosity of the poly( aryl ether )s were 0.10 ~ 1.26 dL/g. The electrochemical properties of the poly( aryl ether )s were investigated by cyclic voltammetry. The energy levels of the HOMO and LUMO were respectively estimated as -5.54 ~ -5.42 eV and -2.52 ~ -2.25 eV, respectively, calculated from the oxidation potentials and onset absorption wavelengths of the UV-vis spectra.