Synergistic effect of thermal crosslinking and thermal rearrangement on free volume and gas separation properties of 6FDA based polyimide membranes studied by positron annihilation.

Two kinds of polyimide membranes 6F-AP and 6F-AP/DA (APAF:DABA=3:2) were synthesized and heated between 300–450 °C to study the effect of thermal treatment on the chain structure and gas transport performance of membranes. Fourier Transform Infrared (FI-IR) and X-ray diffraction (XRD) measurements show that heating causes rearrangement of polyimide into rigid polybenzoxazole which prevents the effective stacking of polymer chains leading to the increase of d-spacing and fractional free volume. Positron annihilation results confirm the increase of both size and number of free volume due to the thermal rearrangement. The addition of DABA monomer into 6F-AP causes crosslinking during heating, which results in tightening of the rigid chain spacing of benzoxazole, thus leading to slight decrease in the size and number of free volume. The increase in fraction free volume induced by thermal rearrangement can significantly improve the gas permeability of 6F-AP series membranes, which increases from 16.2 and 3.9 barrer to 271.4 and 200.3 barrer for H 2 and CO 2 , respectively, after increasing the heating temperature from 300 to 450 °C. But this is accompanied by a decrease in gas selectivity due to the increase in free volume size. Finally, by careful tailoring the free volume structure through thermal rearrangement and crosslinking, the 6F-AP/DA polyimide treated at 400 °C exhibits a H 2 permeability of 196.4 barrer and a H 2 /CH 4 ideal selectivity of 90, which is above the 2008 Robeson upper bound. Our results indicate that by designing the functional groups of the reaction monomer plus appropriate thermal treatment, the microstructure of polyimide membrane can be effectively adjusted for high-performance gas separation. [Display omitted] • Cross-Linked Thermally Rearranged Poly(benzoxazole-co-imide) membranes were prepared by heating at varying temperatures. • Thermal rearrangement and thermal crosslinking had been analyzed to understand the change of free volume of polymers. • The free volume of membranes was accurately measured by positron annihilation. • Cross-Linked TR membrane treated at 400 °C exhibited excellent H 2 /CH 4 separation performance exceeding the 2008 upper bound. [ABSTRACT FROM AUTHOR]