High performance, robust polymeric membranes are playing more and more important roles in recent large scale industrial gas separation applications. One of the biggest challenges is scaling up the high performance polymeric materials. Herein, a one-step super-acid catalyzed condensation reaction was reported to synthesize two novel hydroxyl-functionalized fully carbon main chain intrinsic microporous polymers (HSBI-Is and HBIN-Is) with high efficiency. Both polymers demonstrated high molecular weight, good thermal stability with T_d above 360 °C, and modest microporosity. HSBI-Is exhibited a more open structure with higher BET surface area (523 vs 57 m² g⁻¹), larger fractional free volume (0.212 vs 0.162), and d-spacing (5.16 vs 3.68 Å) than HBIN-Is due to its more rigid and bulky spirobisindane (SBI) site of contortion. Membranes based on HSBI-Is and HBIN-Is showed moderate to high permeabilities and selectivitites with H₂/N₂, H₂/CH₄, O₂/N₂ and CO₂/CH₄ close to or even beat the 2008 trade-off curves. In which, the HBIN-Is showed a remarkable CO₂/CH₄ selectivity of 73.8, and the HSBI-Is demonstrated a remarkable O₂/N₂ selectivity of 10.4 at −20 °C due to the sharply increased diffusion selectivity. Both polymer membranes showed excellent plasticization resistance up to 25 bar upstream pressure, endowing the polymerization method and the hydroxyl functionalized intrinsic microporous polymers of great potential in real gas separation applications.

高性能，坚固的聚合物膜在最近的大规模工业气体分离应用中发挥着越来越重要的作用。最大的挑战之一是扩大高性能聚合物材料的规模。在本文中，据报导，一步式超酸催化的缩合反应可以高效地合成两种新型的羟基官能化的全碳主链本征微孔聚合物（HSBI-Is和HBIN-Is）。两种聚合物均表现出高分子量，良好的热稳定性（T _d高于360°C）和适度的微孔性。HSBI-Is显示出更开放的结构，具有更高的BET表面积（523对57 m ² g ^-1），更大的自由体积分数（0.212对0.162）和d间距（5.16 vs 3.68Å）比HBIN-Is多，因为它的扭曲螺双双茚满（SBI）位置更刚性和更大。基于HSBI-Is和HBIN-Is的膜表现出中等至高的渗透率，并且具有H ₂ / N ₂，H ₂ / CH ₄，O ₂ / N ₂和CO ₂ / CH _4的选择性，接近或什至超过了2008年的交易。关闭曲线。其中，HBIN-Is显示出显着的CO ₂ / CH ₄选择性，为73.8，HSBI-Is显示出显着的O ₂ / N ₂由于扩散选择性急剧增加，因此在-20°C时具有10.4的选择性。两种聚合物膜在高达25 bar的上游压力下均表现出优异的抗增塑性，这赋予了聚合方法和羟基官能化的固有微孔聚合物在实际气体分离应用中的巨大潜力。