Enhancement of CO2 Affinity in a Polymer of Intrinsic Microporosity by Amine Modification

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• 作者：Christopher R. Mason ; Louise Maynard-Atem ; Kane W. J. Heard ; Bekir Satilmis ; Peter M. Budd ; Karel Friess ; Marek Lanc? ; Paola Bernardo ; Gabriele Clarizia ; Johannes C. Jansen
• 刊名：Macromolecules
• 出版年：2014
• 出版时间：February 11, 2014
• 年：2014
• 卷：47
• 期：3
• 页码：1021-1029
• 全文大小：486K
• ISSN：1520-5835

文摘

Nitrile groups in the polymer of intrinsic microporosity PIM-1 were reduced to primary amines using borane complexes. In adsorption experiments, the novel amine鈥揚IM-1 showed higher CO₂ uptake and higher CO₂/N₂ sorption selectivity than the parent polymer, with very evident dual-mode sorption behavior. In gas permeation with six light gases, the individual contributions of solubility and diffusion to the overall permeability was determined via time-lag analysis. The high CO₂ affinity drastically restricts diffusion at low pressures and lowers CO₂ permeability compared to the parent PIM-1. Furthermore, the size-sieving properties of the polymer are increased, which can be attributed to a higher stiffness of the system arising from hydrogen bonding of the amine groups. Thus, for the H₂/CO₂ gas pair, whereas PIM-1 favors CO₂, amine鈥揚IM-1 shows permselectivity toward H₂, breaking the Robeson 2008 upper bound.