Synthesis, characterization, and gas permeation properties of adamantane‐containing polymers of intrinsic microporosity

ABSTRACT A new bis(catechol) monomer, namely, 4,4′‐((1r,3r)‐adamantane‐2,2‐diyl)bis(benzene‐1,2diol) (THADM) was synthesized by condensation of 2‐adamantanone with veratrole followed by demethylation of the formed (1r,3r)‐2,2‐bis(3,4 dimethoxyphenyl)adamantane. Polycondensation of THADM and various compositions of THADM and 5,5,6′,6′‐tetrahydroxy‐3,3,3′,3′‐tetramethylspirobisindane was performed with 2,3,5,6‐tetrafluoroterephthalonitrile (TFTPN) to obtain the homopolymer and copolymers. These polymers demonstrated good solubility in common organic solvents such as dichloromethane, chloroform, and tetrahydrofuran and could be cast into tough films from their chloroform solutions. GPC analysis revealed that number average molecular weights of polymers were in the range 48,100–61,700 g mol−1, suggesting the formation of reasonably high molecular weight polymers. They possessed intrinsic microporosity with Brunauer‐Emmett‐Teller (BET) surface area in the range 703–741 m2 g−1. Thermogravimetric analysis of polymers indicated that 10% weight loss temperature was in the range 513–518 °C demonstrating their excellent thermal stability. THADM‐based polymer of intrinsic microporosity (PIM) showed P(CO2) = 1080, P(O2) = 232 and appreciable selectivity [α(CO2/CH4) = 22.6, α(CO2/N2) = 26.7, and α(O2/N2)= 5.7]. The gas permeability measurements revealed that with increase in the content of adamantane units in PIMs, selectivity increased and permeability decreased, following the trade‐off relationship. The gas separation properties of PIMs containing adamantane units were located close to 2008 Robeson upper bound for gas pairs such as CO2/CH4, CO2/N2, H2/N2, and O2/N2. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 16–24 New adamantane‐containing intrinsically microporous homo‐ and copolymers were synthesized by the polycondensation of (1r, 3r)‐2,2‐bis(3,4‐dihydroxyphenyl)adamantane (THADM) and by varying compositions of THADM and 5,5,6′,6′‐tetrahydroxy 3,3,3′,3′‐tetramethyl‐spirobisindane with 2,3,5,6‐tetrafluoroterephthalonitrile. The gas permeability studies of polymers of intrinsic microporosity demonstrated improvement in selectivity for all gas pairs by the introduction of adamantane units.