Tuning the Molecular Weights, Chain Packing, and Gas-Transport Properties of CANAL Ladder Polymers by Short Alkyl Substitutions

We used catalytic arene−norbornene annulation (CANAL) polymerization to synthesize high-molecular weight (degree of polymerization 500−800 based on Mn) rigid ladder polymers with methyl, ethyl, and isopropyl substituents that can form self-standing films. The short alkyl substitution on CANAL ladder polymers significantly impacted gas transport properties and their chain packing as revealed by variable-temperature pure-gas permeation and high-pressure sorption experiments as well as wide-angle X-ray scattering. Interestingly, a combination of methyl and isopropyl substituents enhanced both the sorption capacity and permeation of all gases tested without compromising permselectivity. Our findings suggest that varying short alkyl substitutions on ladder polymers with high fractional free volume represents an effective strategy to tune their chain packing and fractional free volume, which can enhance permeability without compromising permselectivity.