新型含三苯胺及1,3,4-噁二唑基團之聚醯亞胺之製備與物性研究

Synthesis and Properties of Novel Polyimides Containing Triphenylamine and 1,3,4-Oxadiazole Groups

李建緯(Chien-Wei Li)

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(2009年)

https://doi.org/10.6841/NTUT.2009.00231

摘要

本研究成功合成二種含有三苯胺及1,3,4-噁二唑結構的新型芳香族二胺單體。首先合成新型雙胺N'-(4-aminophenyl)-N'-(4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl)benzene-1,4-diamine後，與一系列的芳香族二酐進行聚縮合反應，可製得一系列三苯胺為主鏈且1,3,4-噁二唑為側鏈的聚醯亞胺。接下來，合成另一個新型雙胺5-(5-(4-(diphenylamino)phenyl)-1,3,4-oxadiazol-2-yl)benzene-1,3-diamine後，以相同方法進行聚縮合反應，可製得另一系列三苯胺和1,3,4-噁二唑為側鏈的聚醯亞胺。其中只有與4,4'-六氟異亞丙基二酞酐(6FDA)進行聚縮合反應所得到的聚醯亞胺（6a, 6a'）溶解性最佳，可溶於大部分極性有機溶劑；其固有黏度分別是0.61和0.25 dL/g。光學性質方面，在10-5 M的三氯甲烷溶液中，6a顯示兩個明顯的吸收峰在293和357 nm，最大螢光放射峰在434 nm。然而，6’a 顯示一個清楚的吸收峰在371 nm，最大螢光放射峰在437 nm。熱性質方面，6系列的聚醯亞胺玻璃轉移溫度介於265-324℃，而6’系列的聚醯亞胺玻璃轉移溫度介於309-319℃，兩者的10％熱烈解溫度顯示出良好的熱穩定性。電化學性質藉由循環伏安圖顯示出二對氧化還原峰，HOMO能量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5.21和5.18 eV。

關鍵字

三苯胺基團 ； 1,3,4-噁二唑基團 ； 聚醯亞胺聚合物

並列摘要

Two novel aromatic diamines consisting of triphenylamine and 1,3,4-oxadiazole groups were successfully synthesized. First, N'-(4-aminophenyl)-N'-(4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl)benzene-1,4-diamine was prepared and polymerization was carried out by direct polycondensation with a series of dianhydrides to obtain polyimides containig triphenylamine units in the main chain and 1,3,4-oxadiazole moieties as pendent group. Next, another novel diamine, 5-(5-(4-(diphenylamino)phenyl)-1,3,4-oxadiazol-2-yl)benzene-1,3-diamine, was prepared and polymerization was carried out in the same way to obtain polyimides containig triphenylamine units and 1,3,4-oxadiazole moieties in the side chain . Only 6a and 6’a polyimides obtained by polycondensing from 4,4'-hexafluoroisopropylidenediphathalic anhydride (6FDA) possessed better solubility, and they could be dissolved in most polar organic solvents. Their inherent viscosities were 0.61 and 0.25 dL/g, respectively. At 10-5 M in chloroform solution, 6a exhibited two distinct absorption peaks around 293 and 357 nm, and maximum fluorescence emission peak at 434 nm. However, 6’a exhibited one obvious absorption peak around 371 nm, and maximum fluorescence emission peak at 437 nm. For thermal properties, Tg values of the 6 series of polyimides containing triphenylamine in the main chain (265－324℃) were lower than 6’ series of polyimides containing triphenylamine in the side chain (309－319℃). Besides, for 10% weight loss of two series of polyimides in nitrogen atmosphere showed excellent thermal stability. The electrochemical properties of the polyimide 6a and 6’a were investigated using cyclic voltammetry (CV) and showed two couples of redox peak. The energy levels of the HOMO were respectively estimated as 5.21 and 5.18 eV from the oxidation potential and the onset absorption wavelength of the UV-vis spectrum.

並列關鍵字

Triphenylamine ； 1,3,4-oxadiazole ； Polyimide

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