Exo-selective, Reductive Heck Derived Polynorbornenes with Enhanced Molecular Weights, Yields, and Hydrocarbon Gas Transport Properties

BJ Sundell and JA Lawrence and DJ Harrigan and SB Lin and TP Headrick and JT O'Brien and WF Penniman and N Sandler, ACS MACRO LETTERS, 9, 1363-1368 (2020).

DOI: 10.1021/acsmacrolett.0c00555

Next-generation membranes use highly engineered polymeric structures with enhanced chain rigidity, yet difficulties in polymerization often limit molecular weights required for film formation. Addition-type polynorbornenes are promising materials for industrial gas separations, but suffer from these limitations owing to endo-exo monomeric mixtures that restrict polymerization sites. In this work, a synthetic approach employing the reductive Mizoroki-Heck reaction resulted in exo-selective products that polymerized up to >99% yields for ROMP and addition-type polymers, achieving molecular weights an order of magnitude higher than addition-type polymers from endo-exo mixtures and impressive side group stereoregularity. Due to this increased macromolecular control, these polynorbornenes demonstrate unique solubility-selective permeation with mixed gas selectivities that exceed commercially used PDMS. In addition to thermal and structural characterization, XRD and computational studies confirmed the results of pure and mixed-gas transport testing, which show highly rigid membranes with favorably disrupted chain packing.

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