微波辐射合成含三苯基吡啶结构超支化聚酰亚胺及其光学性能的研究

利用自己合成的含三苯基吡啶结构的BB′2型芳香三胺TAPP与A2型的二酐3,3′,4,4′-二苯酮四羧酸二酐(BTDA)在微波辐射下经"两步法"分别合成了氨基封端和酐基封端的新型超支化聚酰亚胺(AM-HBPI和AD-HBPI).通过FTIR、1H-NMR、XRD、TGA、溶解性试验以及UV-Vis和荧光光谱等对产物进行了一系列的结构表征和性能测试.结果表明,两种新型的含三苯基吡啶结构超支化聚酰亚胺(HBPI)在强极性非质子溶剂中均显示出良好的溶解性,对无机稀酸也具有一定的抗腐蚀性;它们还体现出优异的耐高温性,在N2中的10%热失重温度(T10%)分别高达573℃和568℃.除此之外,AM-HBPI和AD-HBPI还分别在200～400nm和200～350nm具有良好的紫外光吸收性能,以及紫、蓝色荧光发射性能.而且它们被HCl质子化后的紫外光吸收谱带均扩宽至425nm,荧光发射峰的强度也大大增强.

MICROWAVE-ASSISTED SYNTHESIS AND OPTICAL PROPERTIES OF HYPERBRANCHED POLYIMIDES CONTAINING TRIPHENYLPYRIDINE STRUCTURE

Novel amino-terminated and anhydride-terminated hyperbranched polyimides (AM-HBPI and AD- HBPI) were successfully prepared by the two step method with a BB′2-type aromatic triamine containing triphenylpyridine structure ( TAPP ) and a A2-type dianhydride,3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) under microwave irradiaton. The chemical structure and properties of the resulting HBPIs were characterized by FTIR spectroscopy,1H-NMR spectroscopy,XRD,TGA,solubility test,UV-Vis spectroscopy and fluorescence spectroscopy,respectively. The results showed that the resulting AM-HBPI and AD-HBPI were highly organosoluble in strong polar aprotic solvents and showed certain resistance to dilute inorganic acid corrosion. These polymers exhibited good thermal stability with the 10% weight loss temperature (Td10% ) up to 573℃ and 568℃ in N2 atmosphere,respectively. Furthermore,the obtained AM-HBPI and AD- HBPI containing triphenylpyridine structure exhibited UV-Vis absorption bands in the region of 200 ～ 400 nm and 200 ～ 350 nm,as well as possessed strong purple and blue fluorescence,respectively. The UV-Vis absorption bands both extended to 425 nm and fluorescence intensity increased after the polymers were protonated with hydrochloric acid. As a result,these organosoluble novel hyperbranched polyimides containing triphenylpyridine structure were promising as high temperature resistant materials for organic photoluminescent,etc. ,photoelectric applications.