Enhancing CO2 Transport Across the PEG/PPG‐Based Crosslinked Rubbery Polymer Membranes with a Sterically Bulky Carbazole‐Based ROMP Comonomer

A series of poly(ethylene glycol)-block-poly(propylene glycol) (PEG/PPG)- and 5,6-di(9H-carbazol-9-yl)isoindoline-1,3-dione (2CZPImide)-based crosslinked rubbery polymer membranes, denoted as PEG/PPG-2CZPImide (x:y), are prepared from the norbornene-functionalized PEG/PPG oligomer (NB-PEG/PPG-NB) and 2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-5,6-di(9H-carbazol-9-yl)isoindoline-1,3-dione (2CZPImide-NB) via ring-opening metathesis polymerization (ROMP). The molar ratio (x:y) of the NB-PEG/PPG-NB (x) to 2CZPImide-NB (y) monomers is varied from 10:1 to 6:1. X-ray diffraction (XRD), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), and pure gas permeability studies reveal that the comonomer 2CZPImide-NB successfully increases the d-spacing among the crystalline PEG/PPG segments, hence enhancing the diffusivity of gases through the membranes. The synthesized membranes exhibit good CO₂ separation performance, with CO₂ permeabilities ranging from 311.1 to 418.1 Barrer and CO₂/N₂ and CO₂/CH₄ selectivities of 39.4-52.0 and 13.4-16.0, respectively, approaching the 2008 Robeson upper bound. Moreover, PEG/PPG-2CZPImide (6:1), displaying optimal CO₂ permeability and CO₂/N₂ and CO₂/CH₄ selectivities, shows long-term stability against physical aging and plasticization resistance up to 20 days and 10 atm, respectively.