Crosslinking and stabilization of high fractional free volume polymers for gas separation

Crosslinkable poly(4-methyl-2-pentyne) (PMP) membranes were cast from carbon tetrachloride solutions containing PMP and either 4,4′-diazidobenzophenone or 4,4′-(hexafluoroisopropylidene)diphenyl azide. The composite membranes were transparent and homogeneous and were crosslinked by UV irradiation at room temperature or thermal treatment at 180 °C. Low levels of the bis(aryl azide) (1–4.5 wt%) were effective in rendering the membranes insoluble in cyclohexane and carbon tetrachloride, both are good solvents for PMP, thus PMP can easily be converted to mechanically stable membranes with permeabilities and selectivities comparable or higher than those of the well-known poly(dimethylsiloxane) (PDMS). The permeabilities of O₂, N₂, H₂, CH₄ and CO₂ were measured. Compared to pure PMP, the crosslinked membranes containing bis(aryl azide) had lower permeabilities and higher selectivities, consistent with a reduction in free volume.