Role of side-chain length on gas transport of CO2/CH4 mixtures in polymers with side-chain porosity

Polymers of intrinsic microporosity (PIMs) are traditionally formed from ladder backbones, but recent synthetic advances have allowed for the formation of non-traditional PIMs using a poly(ladder) motif, whereby rigid PIM-like sidechains are appended onto more flexible backbones. The effect of side-chain length on free volume and gas transport properties was recently evaluated for a methoxy-functionalized poly(ladder) (OMe-ROMP). In this study, we elaborate on the role of side-chain length and its influence on mixed-gas performance and plasticization stability for OMe-ROMP. Pure-gas sorption results are also reported, including hysteresis effects from CO 2 conditioning. Taken together, this study reveals the role of side-chain length on gas sorption, diffusion, and plasticization for CO 2 /CH 4 separations. We conclude that the length of a rigid side chain in the poly(ladder) motif is a valuable structural parameter to control sorption, diffusion, and stability towards plasticization for gas separation membrane materials. • Plasticization resistance on OMe-functionalized ROMP polymers was studied. • Increasing side-chain length on polymers led to increased gas sorption. • Mixed-gas CO 2 /CH 4 permeation tests showed increasing plasticization resistance with side-chain length.