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

Sulaiman Aloraini; Michael Mathias; Jessica Crone; Kurtis Bryce; Ming Yu; Richard A Kirk; Mohd Zamidi Ahmad; Edidiong D Asuquo; Sandra Rico-Martínez; Alexey V Volkov; Andrew B Foster; Peter M Budd

doi:10.1021/acsapm.2c01600

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

ACS Appl Polym Mater. 2023 Jan 17;5(2):1145-1158. doi: 10.1021/acsapm.2c01600. eCollection 2023 Feb 10.

Authors

Affiliations

¹ Department of Chemistry, University of Manchester, Oxford Road, ManchesterM13 9PL, United Kingdom.
² Department of Chemistry, College of Science and Arts, Qassim University, Ar Rass52571, Saudi Arabia.
³ Department of Chemical Engineering, The University of Melbourne, Melbourne, VIC3010, Australia.
⁴ IU CINQUIMA, Universidad de Valladolid, Paseo Belén 5, E-47011Valladolid, Spain.
⁵ A. V. Topchiev Institute of Petrochemical Synthesis, 29 Leninsky Avenue, Moscow119991, Russian Federation.

Abstract

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.