De‐carboxylation of cross‐linkable triptycene‐based polyimides for CO₂ separation

AbstractPolymer‐based membrane technology holds immense promise for CO2 separation. However, it faces persistent challenges, including the high CO2 pressure‐induced plasticization and permeability‐selectivity trade‐offs, which significantly hinder the development of polymeric membranes. To tackle this issue, we synthesized a novel polyimide 6FDA‐DAT:DABA(6FDD) containing triptycene and carboxylic groups. Upon de‐carboxylation induced cross‐linking, the membrane demonstrated a simultaneous enhancement of gas permeability and selectivity. Specifically, compared to the uncross‐linked 6FDD, the 400°C‐24 h cross‐linked membrane exhibited a remarkable increase in CO2 permeability by 177% (93.1 Barrer) and a significant rise in CO2/CH4 selectivity by 47% (57.5), reaching the CO2/CH4 upper bound. More importantly, the cross‐linked membrane displayed vastly improved CO2 plasticization resistance, withstanding up to 42 bar of CO2 feed pressure. The design of decarboxylated cross‐linked membranes in this work paves the way for creating high‐performing and plasticization‐resistant membranes with potential applications in high‐pressure CO2 separations.