The synthesis, chain-packing simulation and long-term gas permeability of highly selective spirobifluorene-based polymers of intrinsic microporosity
The synthesis, chain-packing simulation and long-term gas permeability of highly selective spirobifluorene-based polymers of intrinsic microporosity
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DOI：
10.1039/c8ta02601g
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发表时间：
2018-06-14
影响因子：
11.9
通讯作者：
McKeown, Neil B.
中科院分区：
文献类型：
--
作者：
Bezzu, C. Grazia;Carta, Mariolino;McKeown, Neil B.
由固有微孔聚合物（sbf - pim）组成的膜具有商业气体分离的潜力。在此，我们报告了一项模拟和实验相结合的研究，研究了通过在spirobifluor芴衍生的pim （PIM-SBFs）上放置简单取代基（如甲基，t-丁基和熔融苯基）对聚合物微孔隙度和透气性的影响。结果表明，甲基或t-丁基取代基均能显著提高气体渗透率，其中4个甲基能提高1.0 nm超微孔的浓度。长期老化研究（大约3.5年）证明了PIM-SBFs作为气体分离的高性能膜材料的潜力。特别是，由四甲基取代的SBF得到的PIM数据达到了2015年提出的O-2/N-2的Robeson上限，因此，对空气中的氧或氮富集有希望。老化的PIM-SBFs的CO2/CH4混合气体渗透率测量也表明它们具有天然气或沼气升级的潜力。
Membranes composed of Polymers of Intrinsic Microporosity (SBF-PIMs) have potential for commercial gas separation. Here we report a combined simulation and experimental study to investigate the effect on polymer microporosity and gas permeability by placing simple substituents such as methyl, t-butyl and fused benzo groups onto PIMs derived from spirobifluorene (PIM-SBFs). It is shown that methyl or t-butyl substituents both cause a large increase in gas permeabilities with four methyl groups enhancing the concentration of ultramicropores (1.0 nm). Long-term ageing studies (>3.5 years) demonstrate the potential of PIM-SBFs as highperformance membrane materials for gas separations. In particular, the data for the PIM derived from tetramethyl substituted SBF reaches the proposed 2015 Robeson upper bound for O-2/N-2 and, hence, hold promise for the oxygen or nitrogen enrichment of air. Mixed gas permeation measurements for CO2/CH4 of the aged PIM-SBFs also demonstrate their potential for natural gas or biogas upgrading.