本研究成功合成一系列含三吡啶和三苯胺結構之聚醯亞胺共聚物,首先合成新型雙胺單體N-(4-aminophenyl)-N-(4-(2,6-di(pyridin-2-yl)pyridine-4-yl)phenyl)benzene-1,4-diamine後與各種二酐聚合成聚醯胺酸,並利用傳統化學閉環法和熱閉環法進行脫水反應合成聚醯亞胺,並探討其熱性質、光電性質以及溶解性。化學合環(PI)和熱合環(PIT)在氮氣下的5 %重量損失分別在430~536 ℃和483~590 ℃,而10 %重量損失分別在485~586 ℃和521~615 ℃,在氮氣下加熱至800 ℃時的殘餘率超過10 %,玻璃轉移溫度(Tg)則分別是300~317 ℃和309~319 ℃。聚醯胺酸和聚醯亞胺在NMP溶液中,於250~400 nm有UV – vis吸收峰,而在310~600 nm有PL放射峰,隨著滴加不同金屬離子,從UV-vis可以觀察到金屬配體電荷轉移(MLCT)的現象,350~400 nm的吸收峰下降且400-500 nm的吸收峰上升。從PL中可以觀察到隨著滴加不同的金屬離子造成強度下降或是發光偏移的現象。
A series of novel polyimides containing terpyridine and triphenylamine moieties were successfully synthesized. First, N-(4-aminophenyl)-N-(4-(2,6-di(pyridin-2-yl)pyridine-4-yl)phenyl)benzene-1,4-diamine was prepared and polymerized with various tetracarboxylic dianhydrides. The cyclodehydration reaction of polyimides carried out in was two different way. One is chemical cyclodehydration (PI), and the other one is thermal cyclodehydration (PIT). The thermal properties, optical properties and solubility of the polyimides were investigated and discussed. Polyimides derived from chemical cyclodehydration (PI) and thermal cyclodehydration (PIT) showed 5% weight loss temperatures under nitrogen at 430 ~ 536 ℃ and 483 ~ 590 ° C, respectively, and 10% weight loss at 485 ~ 586 ℃ and 521 ~ 615 ° C, the residual rates at 800 ℃ are over 10 %, and the glass transition temperature were about 300~317 ℃and 309~319 ℃. Polyamic acids and polyimides in NMP solution has UV - vis absorption peak at 250 ~ 400 nm. And it occurred PL emission peak at 310 ~ 600 nm. According to different kind of metal ions added, and MLCT (Metal-to-Ligand Charge Trandfer) was observed form UV-vis. The absorption band of terpyridine was observed from 350~400 nm, and the one of metal-chelated terpyridine was observed from 400~500 nm. On the other hand, it was observed that the PL intensity decreased or peak shifted dependent on the added metal ions.
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