Preparation of defect-free asymmetric gas separation membranes with dihydrolevoglucosenone (Cyrene^TM) as a greener polar aprotic solvent

Nonsolvent-induced phase separation (NIPS) is widely used to prepare asymmetric gas separation membranes. Most industrial NIPS casting solution formulations are limited to a small group of glassy polymers and, importantly, require toxic polar aprotic solvents such as N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), or N-methyl-2-pyrrolidone (NMP). Growing restrictions on the use of such solvents are spurring the search for more benign casting solution formulations that do not compromise membrane performance. This study reports high-flux, defect-free asymmetric polysulfone (PSf) gas separation membranes prepared using dihydrolevoglucosenone (Cyrene^TM), a polar aprotic solvent that is believed to be safer than DMAc, DMF, and NMP, as the majority casting solution component. Optimized formulations and casting conditions produce membranes with hydrogen permeances exceeding 100 gas permeance units (GPU) and selectivities at or above those of dense PSf films. Dry/wet NIPS membrane performance improved with shorter dry step times and increased Cyrene^TM loadings relative to the volatile solvent, tetrahydrofuran (THF), in the casting solution. The high water-Cyrene^TM Flory-Huggins interaction parameter, χ₁₂, and high casting solution viscosities help suppress the formation of skin layer defects and sublayer macrovoids. In some cases, membrane selectivities were influenced by substructure resistance, providing insight into the relationship between sublayer morphology and membrane performance.