基于三蝶烯结构D_(3h)对称性聚酰亚胺的合成及性能研究

Synthesis and Properties of Polyimides Derived from Triptycene with D_(3h) Symmetry

以四氯邻氨基苯甲酸和蒽经Diels-Alder反应得到1,2,3,4-四氯三蝶烯,再经硝化、还原得到2,6-二氨基-13,14,15,16-四氯三蝶烯二胺单体.该二胺与双酚A二酐（BPADA）、六氟二酐（6FDA）和3,3＇,4,4＇-二苯甲酮四羧酸二酐（BTDA）经两步法缩聚得到系列聚酰亚胺.对2,6-二氨基-13,14,15,16-四氯三蝶烯二胺单体进行了1H-NMR,13C-NMR,FTIR表征,对所合成聚酰亚胺进行了1H-NMR、FTIR结构表征及溶解性、热性能、特性粘度、BET等测试.结果表明,含四氯三蝶烯结构的聚酰亚胺具有优异的溶解性,能溶于DMAc、DMF、NMP、THF、吡啶、间甲酚等有机溶剂,其中基于双酚A二酐和六氟二酐的聚酰亚胺在室温下能溶于氯仿中.聚合物具有良好的热性能,在0~300℃之间没有发现其玻璃化转变温度以及10%的热失重温度均高于500℃.聚合物可形成颜色较浅的透明薄膜,其中基于双酚A二酐的聚酰亚胺薄膜为无色透明.基于六氟二酐的聚酰亚胺BET比表面积为370 m2/g,是一种新型多孔聚合物.

1,2,3,4-tetrachlorotriptycene was synthesized by Diels-Alder reaction using tetrachlorophthalic acid and anthracene. Then by nitration and reduction of 1 , 2,3,4-tetrachlorotriptycene, 2,6-diamino-13,14, 15,16-tetrachloro triptycene diamine monomer was prepared. Novel triptycene polyimides were synthesized via a two step polycondensation by 2,6-diamino-13,14,15,16-tetrachloro triptycene diamine and bisphenol A dianhydride and hexafluoro dianhydride and 3, 3＇, 4, 4＇-benzophenone tetracarboxylic dianhydride. The structure of 2,6-diamino-13,14, 15,16-tetrachloro triptycene diamine monomer was characterized by I H- NMR, 13 C-NMR and FTIR. The structure of polyimides were characterized by 1H-NMR, FTIR, the properties of the polymers were investigated by solubility, thermal properties, inherent viscosity and BET. The results showed that polyimides containing the tetrachlorotriptycene structure had good solubility,polymers could be dissolved in common organic solvents, such as DMAc, DMF, NMP, THF, pyridine and m-cresol. In particular, polyimides based on bisphenol A dianhydride and hexafluoro dianhydride were easily dissolved in chloroform at room temperature. These polyimides had excellent thermal properties,the glass transition temperature of the polymers was not found between 0 - 300℃ and the 10% weight loss temperatures of these three polyimides were all above 500℃. The three polymimides also had good film forming properties giving light transparent films, wherein the polyimide films based on bisphenol A dianhydride were colorless transparent. The polyimide based on hexafluoro dianhydride with BET specific surface area of 370 m2/g was a novel porous polymer.