Polymers of intrinsic microporosity (PIM) as one of potential next generation membrane materials for gas separation has attracted great interests due to its ultra-permeable characteristics. Herein, a novel bis(phenyl)fluorene-based PIMs (Cardo-PIM-1) based on 9,9-bis(3,4-dihydroxyphenyl) fluorene (BDPF), 2,3,5,6-tetrafluoroterephthalonitrile (TFTPN) and spirocyclic 5,5′,6,6′-tetrahydroxy-3,3′,3,3′-tetramethylspirobisindane (TTSBI) were prepared vis dibenzodioxane polymerization reaction, and then the functionalized multi-walled carbon nanotubes (f-MWCNTs) were incorporated into Cardo-PIM-1 to fabricate mixed matrix membranes (MMMs) with solution mixing method for CO₂ separation. The structure analysis indicated that the MWCNTs were cut into short ropes and the amino groups were incorporated into the nanotubes surface after treated with acid mixtures followed by ethylenediamine modification. FTIR spectroscopy and nuclear magnetic resonance (NMR) measurement confirmed the formation of Cardo-PIM-1 macromolecule. BET and positron annihilation lifetime spectroscopy (PALS) analysis exhibited that Cardo-PIM-1 contained larger pore-size distribution and fractional free volume (FFV), and preferential CO₂ adsorption capacity over N₂ compared with that of PIM-1. This work investigated the structure of polymer as well as the effect of nanofillers in the gas separation performance. High CO₂ permeability of 2.9 × 10⁴ Barrer with a desirable CO₂/N₂ separation factor of 24.2 was achieved using the MMMs with 7.5 wt% f-MWCNTs loading, which were among the best performance for CO₂ separation. The Cardo-PIM-1/f-MWCNTs MMMs will provide a promising alternative in industrial flue gas separation and CO₂ capture process.

具有固有的微孔性（PIM）的聚合物作为潜在的下一代气体分离膜材料之一，由于其超渗透性而引起了人们的极大兴趣。本文中，基于9,9-双（3,4-二羟基苯基）芴（BDPF），2,3,5,6-四氟对苯二甲腈（TFTPN）的新型双（苯基）芴基PIM（Cardo-PIM-1）并通过二苯并二恶烷聚合反应制备了5,5'，6,6'-四羟基-3,3'，3,3'-四甲基螺双茚满（TTSBI），然后将功能化的多壁碳纳米管（f-MWCNTs）与Cardo-PIM-1结合使用CO ₂溶液混合法制造混合基质膜（MMM）分离。结构分析表明，在用酸混合物处理后进行乙二胺改性后，将MWCNT切成短绳，并将氨基结合到纳米管表面。FTIR光谱和核磁共振（NMR）测量证实了Cardo-PIM-1大分子的形成。BET和正电子an没寿命谱（PALS）分析表明，与PIM-1相比，Cardo-PIM-1的孔径分布和自由体积分数（FFV）更大，并且具有比N ₂更好的CO ₂吸附能力。这项工作研究了聚合物的结构以及纳米填料对气体分离性能的影响。2.9×10 ^4的高CO ₂渗透性使用负载量为7.5 wt％f-MWCNT的MMM，获得了理想的CO ₂ / N ₂分离因子为24.2的Barrer ，这是分离CO ₂的最佳性能之一。Cardo-PIM-1 / f-MWCNTs MMM将为工业烟气分离和CO ₂捕集工艺提供有希望的替代方法。