The energy consumption for chemical separations in the US is about 17,000 quadrillion Joule/year, which represents 50% of the energy consumed by the American industry and 15% of the energy consumed by the Country in one year. More in general, 10% of world energy consumption, that is, about 7.5 GJ per person every year, is devoted to chemical separations. Although membrane-based separations would improve the energy efficiency of existing technologies by 90%, membrane processes still represent only 20% of the total separation market. The permeability-selectivity trade-off, long-term polymers instability and difficulty to simultaneously control solubility-selectivity and diffusivity-selectivity are critical issues that hamper the membrane market to further expand. This talk will show how fundamental principles of polymer chemistry and physics can be exploited to remove roadblocks to progress in the field and tailor selectivity and long-term stability in polymer membranes for gas and organic liquid separation. First, the molecular mechanism by which configurational free volume regulates polymer membranes selectivity and physical aging propensity will be discussed. Then, an approach based on blending conventional polymers with hyper-crosslinked porous structures will be presented as a tool to simultaneously reduce physical aging and swelling in glassy polymers. The detailed molecular mechanism underpinning this approach will be elucidated. Finally, the effect of several halogenated moieties on polymer membranes selectivity and stability will be discussed. A few cases study will be presented, highlighting recent progress and still open questions.

Tailoring polymer membranes selectivity and long-term stability using fundamental chemical-physical principles

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ACS Spring 2023

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