Crosslinking of Branched PIM-1 and PIM-Py Membranes for Recovery of Toluene from Dimethyl Sulfoxide by Pervaporation

Branched forms of the archetypal polymer of intrinsic microporosity PIM-1 and the pyridinecarbonitrile-containing PIM-Py may be crosslinked under ambient conditions by palladium(II) acetate. Branched PIM-1 can arise in polymerizations of 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobisindane with tetrafluoroterephthalonitrile conducted at a high set temperature (160 °C) under conditions, such as high dilution, that lead to a lower-temperature profile over the course of the reaction. Membranes of PIM-1 and PIM-Py crosslinked with palladium acetate are sufficiently stable in organic solvents for use in the recovery of toluene from its mixture with dimethyl sulfoxide (DMSO) by pervaporation at 65 °C. With both PIM-1 and PIM-Py membranes, pervaporation gives high toluene/DMSO separation factors (around 10 with a 77 vol % toluene feed). Detailed analysis shows that the membranes themselves are slightly selective for DMSO and it is the high driving force for toluene evaporation that drives the separation.

Citation

Aloraini, S., Mathias, M., Crone, J., Bryce, K., Yu, M., Kirk, R. A., Ahmad, M. Z., Asuquo, E. D., Rico-Martínez, S., Volkov, A. V., Foster, A. B., & Budd, P. M. (2023). Crosslinking of Branched PIM-1 and PIM-Py Membranes for Recovery of Toluene from Dimethyl Sulfoxide by Pervaporation. ACS Applied Polymer Materials, 5(2), 1145–1158. https://doi.org/10.1021/acsapm.2c01600

Sponsors

This work was supported by a British Council Institutional Links grant, No. 351983438 0100 “Development of a membrane method for the recovery of aromatic hydrocarbons from their mixtures with polar solvents” and by EPSRC Programme Grant ep/v047078/1 “SynHiSel”. S.A. is sponsored by Qassim University, Saudi Arabia. M.Y. is grateful for a Manchester–Melbourne dual award PhD studentship funded by the University of Melbourne. E.D.A. was supported by EPSRC grant EP/M001342/1. S.R.-M. received funding through the University of Valladolid Erasmus+ mobility for traineeship scheme and the Spanish Ministry of Sciences, Innovation and Universities (MCIU) FPU grant. The authors thank Anne Davies and Martin Jennings for their assistance in obtaining the elemental analysis. They also thank Carole Webb for her help with the GC analysis. The authors are grateful to Dr. Pavel Izák, Institute of Chemical Process Fundamentals, Prague, Czech Republic, for the design of the pervaporation cell.

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