Polymers with intrinsic microporosity (PIMs) showed the potential to provide highly permeable and highly selective membranes for gas separation applications with the ability to fine-tune their properties for better performance. The concept of microporosity was extended to the polyimides by using kinked, contorted and stable structures to obtain high gas performance combined with excellent solution-processability, high thermal stability, and a unique platform for a wide range of possible modifications and tunability. Thus, studying the structure-property relationships is a critical key to develop advanced materials that can replace the commercially available membranes like cellulose acetate and Matrimid. Importantly, in the microporous polyimides (PIM-PIs) system, varying the type of the side chains appended to the diamines or dianhydrides impacts polymeric membrane properties, and in turn, gas separation performance.
In this dissertation, we have examined the effect of ring substitutes, incorporated into novel polyimides backbones, on polymer properties and gas separation performance. The choice of side group can induce subtle changes in material properties and molecular interactions between the polymeric chains and affect the pore-size distribution, chain packing and yielding distinct combination between gas permeability and permselectivity.
We have shown that the effect of tertiary amine groups, in polyimide structures, on the CO2 solubility is marginal but it can control the chain packing. However, introducing bromine groups on the polymer backbone can boost the O2 permeability and O2/N2 selectivity and perform better than the commercially available membranes. BCBr4-SBIDA demonstrated the same O2/N2 selectivity relative to cellulose acetate but approximately 10-fold higher gas permeability. Combining high selectivity with good permeability was achieved by a newly designed carboxyl-functionalized homopolymer (6FDA-TrMPD) with CO2 permeability of 144 barrer and CO2/CH4 selectivity of 45. The new W-shaped CANAL diamines, prepared by one-step synthesis, were used as microporosity generators in polyimides and revealed promising gas transport performance with the same selectivity relative to cellulose acetate by 23-fold higher permeability (CANAL-PI-3-MeNH2). Therefore, developing advanced polymers for membrane-based gas separation can be obtained by an ideal combination between kinked monomers, side chains, and stable materials.