(349b) Installing Ladder Motifs in Polymers for Gas and Solvent Separations

Over the last two decades, a variety of new synthesis strategies have been implemented to incorporate monomer residues without rotatable bonds into polymer backbones. This approach produces ultra-glassy materials, measurable BET surface areas, and ultra-high permeabilities. This presentation highlights several of these strategies, including the formation of functionalized polymers of intrinsic microporosity (PIMs), catalytic arene–norbornene annulation (CANAL) polymers, microporous poly(arylene ether)s, and interfacially polymerized PIMs. Structure–property results are highlighted to demonstrate how ladder motifs can be used to significantly improve transport performance for hydrogen, CO₂, and solvent-based separations. In many cases, these polymers have combinations of permeability and selectivity that are among the best of all materials reported within their class. Multi-component results will be presented to show how microporous polymers exhibit unusual and sometimes beneficial effects of competitive sorption, and long-term aging experiments will be presented to highlight how permeability can change and be manipulated for materials that are well below their glass transition temperatures. Finally, a short perspective on scaling and leveraging these materials in industrial applications will be presented.