Abstract
Crosslinking of polymeric membranes induces changes in both membrane stability and separation performance. Numerous membrane-crosslinking methods have been developed with the objective of obtaining improved membranes. However, none of these methods systemically investigated the stereochemical effects of the crosslinker in the pursuit of better stability and performance. Herein, we address this knowledge gap by presenting a systematic investigation of the stereochemistry of crosslinkers. The intrinsically microporous poly(ether-ether-ketone)-containing Troger's base (iPEEK-TB) was synthesized and employed in the fabrication of organic solvent nanofiltration (OSN) membranes. Crosslinkers were carefully selected based on the stereochemical position of the two benzyl bromide functional groups, separated by distances of 4.3, 8.2, 8.5, and 12.4 angstrom and significant effects arising from crosslinking on membrane physical properties, morphology, and OSN performance were investigated. Crosslinked membranes showed excellent solvent resistance, mechanical flexibility, and thermal stability. As a function of crosslinking distance, the molecular weight cutoff (MWCO) values of the membranes varied in the range of 575-750 g mol(-1). The para isomer of the crosslinkers resulted in higher permeance relative to membranes crosslinked with their counterpart ortho isomers, and vice versa, the ortho substitution resulted in higher solute rejection values compared with para isomers. An increase of 50% and 12% in acetonitrile permeance relative to the annealed benchmark membrane was observed upon the treatment using iPEEK-TB with 4,4'-bis(bromomethyl)biphenyl (p-BBMBP) and 2,2'-bis(bromomethyl)-1,1'-biphenyl (o-BBMBP), respectively, whereas a permeance decrease of approximately 23% and 32% was noted upon treatment with alpha,alpha'-Dibromo-p-xylene (p-DBX) and alpha,alpha'-Dibromo-o-xylene (o-DBX), respectively. The corresponding MWCO changes were found to decrease for all crosslinked membranes within the range of 12%-40%. The crosslinked membranes demonstrated stable performance in polar aprotic solvents such as N,N-dimethylformamide and N-methyl-2-pyrrolidone. The Molecular dynamic (MD) simulations supported the obtained performance results through the variations in the fractional free volume (FFV). This work demonstrates the importance of crosslinker selection for OSN membrane performance and solvent resistivity and opens new avenues for fine-tuning membrane stability and OSN performance.