Polymers of intrinsic microporosity containing aryl-phthalimide moieties: synthesis, modeling, and membrane gas transport properties

Abstract

High-performance polymers for membrane gas separation require the careful design of the structure-porous relationship. In this work, five phthalimide-based polymers of intrinsic microporosity (PIMs) were obtained via the double nucleophilic aromatic substitution with the commercially available 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethylspirobisindane (TTSBI) monomer. The phthalimide monomers were synthesized considering different sizes and positions of the alkyl-substituents to evaluate their influence on the physical properties of the polymers and their potential use as gas separation membranes. Four polymers were soluble in the low-boiling solvents chloroform and tetrahydrofuran, facilitating the casting of self-standing films to evaluate their gas separation properties. The thermally stable membranes showed 5% weight lost between 537 °C and 549 °C. As powders, these four polymers showed apparent BET surface areas ranging from 434 to 661 m² g⁻¹. The experimental BET surface areas correlated with those obtained by molecular simulation models of the synthesized polymers. A linear function is proposed as a tool to predict, with a known uncertainty, the surface area values of this type of polymer from the corresponding computational models. As a trend, increasing the volume of the ortho-substituent in the aryl-phthalimide group increases the permeability of the membranes, reaching generally better performances than Matrimid® and close to those of PIM-1, considering their place on the Robeson diagrams of the O₂/N₂, CO₂/CH₄ and CO₂/N₂ gas pairs. Aging studies between 63 and 122 days showed a decrease in permeability, accompanied by the typical increase in selectivity that tends to move the data parallel to the upper Robeson limits.