Mechanical, thermal and gas separation properties of copolyimides and their thermal rearrangement copolymer membranes with spirobisindane structures

Abstract

In this work, two kinds of dimaine monomers with spirocyclic structures, including 3,3,3′,3′-tetramethyl-6,6′-bis[3-amino-4-hydroxyphenoxy]-1,1′-spirobisindane (TBAHS) and 3,3,3′,3′-tetramethyl-bis(5-amino-6-hydroxyphenyl)-1,1′-spirobisindane (TBHAS) are firstly synthesized. Then, the two diamines TBAHS and TBHAS are copolymerized in different molar ratios with equimolar 4,4′-(hexafluoroisopropenyl)diphthalic anhydride (6FDA) to synthesize poly(amic acid) (PAA) solution, followed by thermal imidization to obtain a series of copolyimide (coPI) membranes. Next, these coPI(TBAHS-TBHAS) specimens are subjected to thermal rearrangement (TR) treatment at 450°C to obtain the corresponding coTR(TBAHS-TBHAS) copolymer membranes. The influences of the molar ratio of TBAHS to TBHAS, thermal treatment temperature and time on the microstructures and properties of the PI and TR copolymers are investigated. With the increase of rigid TBHAS molar ratio, the glass transition temperature ( Tg) and d-spacing value of the coPI(TBAHS-TBHAS) samples are significantly enhanced. Furthermore, as the thermal treatment temperature increases, the mechanical properties of the copolymer membranes display a sharply decline trend, but the d-spacing values are obviously increased. When the molar ratio of TBAHS to TBHAS is 7:3, the gas permeabilities of the coTR membrane reach 1140.5, 1180.6, 306.6, and 44.9 Barrer for H2, CO2, O2, and N2, respectively. Meanwhile, the ideal selectivity of O2/ N2 is 6.82, suggesting a superior separation performance close to the 2015 upper limit. Furthermore, with the increase of thermal treatment temperature and time, the gas permeabilities are also improved.