基于含可交联侧基单体的超支化聚酰亚胺多孔材料的设计与构筑

Porous hyperbranched polyimide materials have attracted remarkable attention, because of their large surface area, superior chemical and thermal stability. However, the synthesis of porous hyperbrached polyimide materials has been restricted to the one-step gel polymerization to date, and the porous structure of the polymer materials is difficult to regulate during the process of polymerization reaction. Moreover, there are few types of monomers could be used to construct porous hyperbranched polyimide materials which possess high surface area through one-step gel polymerization. The purpose of this project is to design some novel dianhydrides containing crosslinkable pendant groups and regulate the porous structure of crosslinked hyperbranched polyimide materials by varying the length of pendant groups. In this project, we want to prepare porous hyperbranched polyimide materials through a two-step polymerization method. In the first step, the hyperbranched polyimide skeleton is synthesized by polycondensation reaction between dianhydrides containing crosslinkable pendant group and aromatic multi-amine monomers. In the second step, the porous structure is formed in the hyperbranched polimide skeleton through crosslinking reaction. The porous structure of crosslinked hyperbranched polyimide materials could be regulated by varying the hyperbranched polyimide skeleton, length of pendant group and degree of crosslinking. We hope to investigate the influence of polymer skeleton and degree of crosslinking etc. on the porous structure and adsorption properties, and learn the regulating rules of porous structure and properties of crosslinked hyperbranched polyimide materials. Finally, we hope that the research of crosslinked hyperbrached polyimides could lay the theoretical and experimental foundation for the design and construction of porous high performance polymer materials.

超支化聚酰亚胺多孔材料由于其较大的比表面积以及良好的化学和热稳定性，受到了研究者的关注。目前报道的超支化聚酰亚胺多孔材料主要采用一步凝胶聚合方法进行制备，单体种类与聚合物结构单一，并难于进行孔结构的调控。本项目提出设计合成具有可交联侧基的酸酐单体，通过改变侧基长度实现超支化聚酰亚胺多孔材料孔结构的调控。通过两步聚合的方法，第一步将设计合成的具有可交联侧基的二酐单体与芳香多元胺单体缩聚形成超支化聚酰亚胺骨架，第二步采用二次交联聚合方法使聚合物获得多孔结构，通过改变超支化聚酰亚胺骨架结构、侧基长度和交联密度获得孔结构可调的交联超支化聚酰亚胺多孔材料。研究聚合物骨架结构、交联密度等因素对聚合物孔结构和吸附性能的影响，理解超支化聚酰亚胺多孔材料的孔结构与性质的调控规律，为高性能聚合物多孔材料的设计与构筑奠定理论与实验基础。

超支化聚酰亚胺因其优异的热稳定性和化学稳定性、突出的骨架稳定性和广泛的应用性而得到大量关注。本项目拟解决超支化聚酰亚胺材料孔结构调控等科学问题，以设计、制备及研究新型超支化聚酰亚胺材料为目标，通过改变超支化聚酰亚胺骨架结构、交联结构、交联密度等对交联超支化聚酰亚胺孔结构进行调控，提高聚合物的吸附性能。.设计并合成了具有不同可交联炔基侧基的二酐单体，具有双可交联炔基侧基的二酐单体，具有不同取代基的三胺单体，具有不同结构的卟啉基四胺单体等砌块分子。基于这些单体，通过两步聚合方法制备了具有不同骨架结构的交联超支化微孔聚酰亚胺孔材料、具有不同侧基的交联超支化微孔聚酰亚胺孔材料、不同取代基的交联超支化微孔聚酰亚胺材料、不同的炔基交联型卟啉基微孔聚酰亚胺材料等多个系列的交联微孔聚酰亚胺材料。.经过系统的研究，获得交联超支化微孔聚酰亚胺孔结构的调控规律，并制备了具有良好孔径参数和优异气体吸附性能的交联型超支化微孔聚酰亚胺材料。