Nitrile groups in the polymer of intrinsic microporosity PIM-1 were reduced to primary amines using borane complexes. In adsorption experiments, the novel amine-PIM-1 showed higher CO uptake and higher CO/N 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 CO affinity drastically restricts diffusion at low pressures and lowers CO 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 H/CO gas pair, whereas PIM-1 favors CO, amine-PIM-1 shows permselectivity toward H, breaking the Robeson 2008 upper bound.
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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC4027542 | PMC |
| http://dx.doi.org/10.1021/ma401869p | DOI Listing |
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