The perfluoropolymer upper bound

Abstract Perfluoropolymers have fundamentally distinct thermodynamic partitioning properties compared to those of their hydrocarbon counterparts. However, current upper bound theory assumes hydrocarbon solubility behavior for all polymers. Herein, the fundamental presupposition of invariance in solubility behavior to upper bound performance is critically assessed for perfluoropolymers and hydrocarbon polymers. By modifying solubility relationships, theoretical perfluoropolymer upper bounds are established, showing a positive shift of the upper bound front as a result of beneficial solubility selectivities for certain gas pairs, including N 2 /CH 4 , He/H 2 , He/N 2 , He/CH 4 , and He/CO 2 . Within the framework of the solution–diffusion model, an analysis is presented to compare two independent approaches often pursued in efforts to surpass the polymer upper bound: (a) achieving solubility selectivity via perfluoropolymers and (b) improving diffusion selectivity via rigid hydrocarbon polymers. This analysis demonstrates the significant benefit that can be achieved by considering both the chemical composition and morphology of solid‐state macromolecules when designing membrane materials.