Membrane-integrated gas separation is of great interest due to its energy-saving and economic merits. Although easy-to-process polymer membranes have shown potential, insufficient gas permeation and low stability in harsh environments limit their use in practical applications. Here, we demonstrate nanoporous and rigid semi-interpenetrating polymer networks (SIPNs) by incorporating crosslinked network into polymer matrices, accompanying interpenetration and thermal rearrangement (TR) to construct an optimized microporous structure where nanometric and sub-nanometric pores coexist parallel to the gas transport direction. The resulting TR-SIPN improves gas transport without sacrificing separation efficiency since the nanometric and sub-nanometric pores serve as molecular highways and selective bottlenecks, respectively. Furthermore, the plasticization resistance against condensable gases was enhanced due to improved polymer rigidity of the TR-SIPNs. Our study suggests wide applicability of polymer membranes for aggressive gas separations such as natural gas sweetening and olefin/paraffin separation.

膜集成气体分离由于其节能和经济优势而备受关注。尽管易于加工的聚合物膜已显示出潜力，但在恶劣环境中的气体渗透性不足和稳定性低，限制了其在实际应用中的使用。在这里，我们通过将交联网络结合到聚合物基质中，并伴随着互穿和热重排（TR）来构建优化的微孔结构，从而证明了纳米孔和刚性半互穿聚合物网络（SIPNs），其中纳米和亚纳米孔与气体传输平行并存方向。最终的TR-SIPN在不牺牲分离效率的情况下改善了气体传输，因为纳米孔和亚纳米孔分别用作分子通道和选择性瓶颈。此外，由于提高了TR-SIPNs的聚合物刚度，增强了其对可冷凝气体的抗塑化性。我们的研究表明，聚合物膜广泛适用于腐蚀性气体的分离，例如天然气脱硫和烯烃/石蜡的分离。