Using intermolecular interactions to crosslink PIM-1 and modify its gas sorption properties

Abstract

The intermolecular interactions between the "polymer of intrinsic microporosity" PIM-1 and polycyclic aromatic hydrocarbons (PAHs) have been investigated with the aim of modifying the gas sorption and physical properties. Mixing PIM-1 with selected PAHs resulted in rapid precipitation of polymer. Blending PIM-1 with pyrene had a significant effect of the gas sorption properties of the resulting films; dramatically reduced N 2 uptake (77 K), whilst CO 2 uptake at 298 K was only slightly reduced. A gateopening behaviour was also observed for the N 2 gas sorption (77 K), which was related to the pyrene content of the blend. Using an electron-donating PAH as the additive resulted in a stronger interaction.By exploiting a post-modification strategy after PIM-1 film formation, the absorption of either pyrene or 1-aminopyrene produced films with higher elastic moduli and greatly improved CO 2 /N 2 gas sorption selectivities (293 K). Single gas permeability measurements revealed that while the 1-aminopyrene modified film possessed reduced CO 2 permeability, it possessed enhanced CO 2 /N 2 selectivity. Importantly, the ageing of the permeability was halted over the 50 days tested, likely due to the physical crosslinking of the polymer chains by 1-aminopyrene. † Electronic supplementary information (ESI) available: The ESI contains further photographs investigating the precipitation of PIM-1 into solutions of pyrene. Dynamic light scattering analysis of PIM-1 precipitation with pyrene, gas sorption data comparing the effect of length of time used for the methanol soaking of PIM-1 lms, a photograph of PIM-1 and PAH blends dried to give lms, UV-Vis data for the relationship between pyrene concentration in solution and the amount of pyrene absorbed by the PIM-1 lm, visual and SEM comparison of post-modied PIM-1 lms, and transmission UV-Vis of PIM-1 lms post-modied with pyrene. See

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