含有三蝶烯結構的聚醯亞胺之合成與性質

Synthesis and Properties of Triptycene-containing Polyimides

陳文正(Wenjeng Chen)

指導教授 ： 蕭勝輝

國立臺北科技大學/工程學院/化學工程研究所/碩士(2010年)

摘要

兩種具有三蝶烯結構的新型二胺單體 1,4-bis(4-aminophenoxy)triptycene (4)和1,4-bis(4-amino-2-trifluoromethylphenoxy)triptycene (6)，可藉由1,4-dihydroxytriptycene分別與p-chloronitrobenzene和2-chloro-5- nitrobenzotrifluoride在碳酸鉀的共存下進行親核性氯基取代反應，然後利用鈀催化聯胺還原法將二硝基中間產物還原而製得。這兩種新型二胺可與市售的六種芳香族二酸酐進行傳統的熱閉環法與化學閉環法聚合而得到具有三蝶烯結構的兩系列聚醯亞胺8a-f和9a-f。這些聚醯亞胺皆具有高的分子量，它們都能被製成具有撓曲性以及良好機械性質的薄膜。在聚醯亞胺的骨架中導入三氟甲基可改善其溶解性，而不會降低其他物理性質。大部分從含氟單體6所得到的聚醯亞胺，尤其是那些藉由化學閉環法所得到的聚醯亞胺，可溶於非質子型的極性溶劑中。一般而言，與結構類似的8系列相比較時，具有三氟甲基取代的9系列聚醯亞胺展現出較淡的顏色及稍低的玻璃轉移溫度(Tg)，但其熱穩定性相近。這些含氟聚醯亞胺9a-f具有272-335 ℃的高Tg值，它們在氮氣或空氣的氣氛中於500℃以前並沒有明顯的裂解現象。由二胺單體6與二酸酐ODPA 和6FDA 所衍生出的含氟聚醯亞胺9d和9f可製成接近無色的薄膜。

關鍵字

聚醯亞胺 ； 三蝶烯 ； 三氟甲基 ； 溶解性 ； 熱性質 ； 光學透明性

並列摘要

Two new triptycene containing bis(ether amine)s, 1,4-bis(4-aminophenoxy)triptycene (4) and 1,4-bis(4-amino-2-trifluoromethylphenoxy)- triptycene (6), were synthesized respectively from the nucleophilic chloro-displacement reactions of p-chloronitrobenzene and 2-chloro-5-nitrobenzotrifluoride with 1,4-dihydroxytriptycene in the presence of potassium carbonate, followed by palladium-catalyzed hydrazine reduction of the dinitro intermediates. The newly synthesized bis(ether amine)s were polymerized with six commercially available aromatic tetracarboxylic dianhydrides to obtain two series of novel triptycene-based polyimides 8a-f and 9a-f by using a conventional two-step synthetic method via thermal and chemical imidization. All the resulting polyimides exhibited high enough molecular weights to permit the casting of flexible and strong films with good mechanical properties. Incorporation of trifluoromethyl groups in the polyimide backbones improves their solubility without decreasing their physical properties. Most of the polyimides derived from the fluorinated monomer 6, especially those prepared via the chemical imidization method, were soluble in aprotic polar solvents. In general, the trifluoromethyl-substituted 9 series polyimides showed a reduced color intensity, a slightly lowered glass-transition temperature (Tg), and comparable thermal stability as compared to the corresponding 8 series analogs. The fluorinated polyimides 9a-f showed high Tg in the range of 272–335 oC and did not reveal significant decomposition before 500 oC in nitrogen or in air. The fluorinated polyimides 9d and 9f derived from diamine 6 with 4,4’-oxydiphthalic anhydride (ODPA) and 4,4’-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), respectively, could afford almost colorless thin films.

並列關鍵字

polyimides ； triptycene ； trifluoromethyl group ； solubility ； thermal properties ； optical transparency

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