具有热致刚性稳态结构的多孔气体分离膜的设计及传递机制研究

Gas membrane separation technology as the most promising new gas separation technology, the high throughput and selectivity of membane materials is the key to large-scale industrial applications. However, the commercial polymeric membrane materials is clearly not meet this requirement because of their defects. Therefore, the investigation and development of new high-performance gas separation membrane materials are still an important research direction in the field of membrane technology. In the item, from the view of molecular structure design, several kinds of new porous gas separation membrane materials with high free-volume elements and thermally induced rigidity and steady-state structure is put forward to be designed and synthesized. Interpretation of forming the rigid and steady-state structure of the polymer film during the heat treatment will be provided, and the formation, evolution and law of microstructure and free volume or pore structure will be explained. The relationship between microstructure and gas separation performance of membranes will be investigated. And the gas delivery mechanism in the new separation membranes will be studied. By optimizing the chemical structure of the polymer procursor, controlling the scale and distribution of free volume in polymer membrane during the thermally induced reaction, the high-performane porous gas separation membrane materials with thermally induced rigidity and steady-state stucture will be prepared. Implementation of the project for the development of new high-performance gas separation membrane materials to promote large-scale industrial application of gas separation membranes have important academic significance and practical value.

气体膜分离技术作为最具发展前景的新型气体分离技术，其膜材料的高通量、高选择性是膜技术实现大规模产业化应用的关键。然而，目前已商业化应用的聚合物膜材料因本身的缺陷显然达不到这一要求。因此，研究开发新型高性能气体分离膜材料依然是膜技术领域的重要研究方向。本课题从分子结构设计出发，设计、合成出几种具有高自由体积，并可在热处理过程中转化为刚性稳态结构的新型多孔聚酰亚胺膜材料；诠释聚合物膜在热处理形成刚性稳态结构过程中的结构、构型及自由体积或孔结构的形成、演变过程及规律；探究膜结构与分离性能的关系；揭示气体在分离膜中的渗透传递机制。通过优化设计聚合物的化学结构，精细控制在热交联反应过程中聚合物自由体积的尺度与分布，制备出高性能具有热致刚性稳态结构的多孔气体分离膜材料。本项目的实施对于开发新型高性能气体分离膜材料，推动气体分离膜大规模产业化应用具有重要的学术意义和实际应用价值。

气体膜分离技术作为最具发展前景的新型气体分离技术，其膜材料的高通量、高选择性是膜技术实现大规模产业化应用的关键。然而，目前已商业化应用的聚合物膜材料因本身的缺陷显然达不到这一要求。因此，研究开发新型高性能气体分离膜材料依然是膜技术领域的重要研究方向。本课题从二胺单体的分子结构设计出发，合成出几种具有高自由体积，并可在热处理过程中转化为刚性稳态结构的新型聚酰亚胺材料，并对其结构与性能间的构效关系进行研究；制备出具有热致刚性稳态结构的多孔气体分离膜材料，并对热处理氛围、温度、组成和结构对分离膜材料结构与性能的影响进行研究；揭示热致重排机理及气体在分离膜中的渗透传递机制。研究结果表明，已经成功合成出5种含邻羟基的二胺单体，包括：3,3'-二氨基双酚芴、3,3'-二氨基酚酞、3,3,3',3'-四甲基-5,5'-二氨基-6,6'-二羟基-1,1'-螺旋双茚满、3,3’-二氨基-4,4’-二羟基四苯基甲烷和9,9’-双(3-氨基-4-羟基苯氧基苯基)芴。对聚酰亚胺的光学性能、力学性能和热性能等进行了表征，表明所合成的聚酰亚胺均表现出良好的综合性能。通过优化聚酰亚胺的结构和组成，可以调控聚酰亚胺基体的结构和性能。随热处理温度升高，分离膜的气体渗透性提高，但选择性有所降低，且氧气氛围会阻碍热致重排反应的发生。5种含羟基二胺单体由于具有较大的空间位阻，赋予气体分离膜优异的气体渗透性能；由于重排后的结构刚性较强，分离膜仍保持了优异的气体选择性；通过增加二胺单体的柔性，可以降低其热致重排反应温度，并有利于保持分离膜的机械性能。综上，本项目的实施对于开发新型高性能气体分离膜材料，推动气体分离膜大规模产业化应用具有重要的学术意义和实际应用价值。