Abstract

A series of thianthrene-5,5,10,10-tetraoxide-containing polyimides with great chain stiffness were prepared and their gas permeation properties were investigated. TADATO/DSDA(1/1)–DDBT copolyimide, which was prepared from thianthrene-2,3,7,8-tetracarboxylic dianhydride-5,5,10,10-tetraoxide (TADATO), 3,3′,4,4′-diphenylsulfonyltetracarboxylic dianhydride (DSDA) and 3,7-diamino-2,8(6)-dimethyldibenzothiophene sulfone (DDBT), displayed much higher CO 2 permeability coefficient ( P CO 2 ) than both DSDA–DDBT and TADATO–DDBT homopolyimides, but their ideal selectivity ( P CO 2 / P N 2 ) were similar. The higher CO 2 permeability coefficient of TADATO/DSDA(1/1)–DDBT was attributed to the higher diffusion coefficient as well as a little higher solubility coefficient. The separation performance of TADATO/DSDA(1/1)–DDBT toward CO 2/N 2 fell above the “upper bound” line, indicating the highest separation performance among the glassy polymer membranes developed so far. Furthermore, this polyimide showed a significantly higher selectivity of CO 2 over N 2 for mixed gas permeation than for single gas permeation (single gas: P CO 2 / P N 2 =35, mixed gases: P CO 2 / P N 2 =49, at 35°C and 2 atm). The “dual-mode” model was used to describe gas sorption and transport behaviors in the membrane.

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