Understanding the Topology of the Polymer of Intrinsic Microporosity PIM-1: Cyclics, Tadpoles, and Network Structures and Their Impact on Membrane Performance

Andrew Foster, Marzieh Tamaddondar, José Luque-Alled, Wayne Harrison, Ze Li, Patricia Gorgojo, Peter Budd

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Abstract

The synthesis of PIM-1 is reported from step growth polymerizations of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane (TTSBI) with the commercially cheaper monomer, tetrachloroterephthalonitrile (TCTPN). Nitrogen purged polymerizations (100 - 160 C) were quenched after a monitored increase in viscosity. A combination of multiple detector SEC, NMR, MALDI TOF, DLS and elemental analysis was used to elucidate significant structural differences (cyclic, branched, tadpole, extended and network topologies) in the polymers produced under different conditions. A significant proportion of the apparent surface area (up to 200 m2 g-1) associated with PIM-1 can be attributable to whether its contorted polymer chains in fact link to form cyclic or other non-linear structures. Membranes cast from solutions of polymer samples containing higher branching and network content exhibited higher gas pair selectivities (CO2 / CH4 and CO2 / N2), above the Robeson 2008 upper bound. A toolbox approach to the characterization and production of topologically different PIM-1 samples has been developed which can be used to tune membrane performance for gas separation and other applications.
Original languageEnglish
Pages (from-to)569-583
Number of pages15
JournalMacromolecules
Volume53
Early online date7 Jan 2020
DOIs
Publication statusPublished - 7 Jan 2020

Keywords

  • polymers of intrinsic microporosity
  • cyclic polymers
  • tadpole polymers
  • polymer topology
  • gas separation membranes
  • thin film composites

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