Role of Grafting Density and Nitrile Functionalization on Gas Transport in Polymers with Side-Chain Porosity

This study details the enhancement of CO2 selectivity in ring-opening metathesis polymerization (ROMP) polymers that contain nitrile moieties and micropore-generating ladder side chains. A material, CN-ROMP homopolymer, with nitriles in the ladder side chains was originally targeted and synthesized; however, its low molecular weight and backbone rigidity precluded film formation. As a result, an alternative method was pursued wherein copolymers were synthesized using norbornene (N) and nitrile norbornene (NN). Herein, we report an investigation of the structure–property relationships of backbone functionalization and grafting density on the CO2 transport properties in these ROMP polymers. Nitrile-containing copolymers showed an increase in CO2/CH4 sorption selectivity and a concomitant increase in CO2/CH4 permselectivity when compared to the unfunctionalized (nitrile-free) analogues. The stability in CO2-rich environments is enhanced as grafting density of the rigid, pore-generating side chains increases and an apparent tunability of CO2 plasticization pressure was observed as a function of norbornene content. Lower loadings of norbornene resulted in higher plasticization pressure points. Gas permeability in the ROMP copolymers was found to correlate most strongly with the concentration of the ladder macromonomers in the polymer chain.