Certain polymers with very high free volume demonstrate a continuous network of interconnected void spaces due to the shape and rigidity of its macromolecular composition; as such, it becomes an intrinsic property for these polymers otherwise seen as polymers of intrinsic microporosity (PIM). Methylated polymers of intrinsic microporosity (PIM-M), bromoalkylated PIM (PIM-BM-x), and thermally self-cross-linked PIM-BM-x were designed and prepared for gas separation performance enhancements. The PIM-BM-x polymeric membranes demonstrated exceptional gas separation performance compared with PIM-M and surpassed the 2008 Robeson upper bound line, that is, the selectivities of PIM-BM-100 membrane for CO₂/CH₄ and O₂/N₂ were as high as 25.8 and 5.6, respectively. The gas permeability testing indicated that the permeability of CO₂ and O₂ for the cross-linked PIM-BM-70 was 48.3 and 11.1 barrer, respectively, while the selectivities of CO₂/CH₄ and O₂/N₂ were, respectively, 43.9 and 6.5 after self-cross-linking at 300 °C for 5 h. More importantly, the cross-linked membrane showed excellent antiplasticization ability with a plasticization pressure higher than 500 psi. This value is relatively greater than the pristine uncross-linked PIM-BM membrane (100 psi).

中文翻译：

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具有疏松取代基和交联键用于气体分离膜的本征微孔聚合物

某些具有很高自由体积的聚合物由于其大分子组成的形状和刚性而表现出相互连接的空隙空间的连续网络。因此，它成为这些聚合物的固有特性，否则被视为固有微孔性（PIM）聚合物。设计并制备了具有固有微孔性（PIM-M），溴烷基化PIM（PIM-BM-x）和热自交联PIM-BM-x的甲基化聚合物，以提高气体分离性能。与PIM-M相比，PIM-BM-x聚合物膜表现出出色的气体分离性能，并超过了2008年的Robeson上限，即PIM-BM-100膜对CO ₂ / CH ₄和O ₂ / N的选择性₂分别高达25.8和5.6。气体渗透性测试表明，交联的PIM-BM-70的CO ₂和O ₂的渗透性分别为48.3和11.1 barrer，而CO ₂ / CH ₄和O ₂ / N ₂的选择性分别为，43.9和6.5在300°C自交联5小时后。更重要的是，该交联膜具有优异的抗塑化能力，其塑化压力高于500 psi。该值相对大于原始的未交联的PIM-BM膜（100 psi）。