Spiro[fluorene-9,9′-xanthene]-containing copolymers of intrinsic microporosity: synthesis, characterization and gas permeation properties

Abstract In the present study, a new bis(catechol) containing spiro[fluorene-9,9′-xanthene], namely, 4,4′-(spiro[fluorene-9,9′-xanthene]-2′,7′-diyl)bis(benzene-1,2-diol) (THSFX) was designed and synthesized. Polycondensation reactions of THSFX and varying compositions of THSFX and 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethyl-1,1′-spirobisindane (TTSBI) were carried out with 2,3,5,6-tetrafluoroterephthalonitrile (TFTPN) to obtain a homopolymer and copolymers, respectively. The organo-soluble polymers exhibited reasonably high molecular weights (23300–34,100 g/mol) and could be cast into self-standing films from their chloroform solutions. X-Ray diffraction studies indicated that PIMs were amorphous in nature. These polymers exhibited high thermal stability (T 10  = 490–510 °C) and possessed intrinsic microporosity with high BET surface area (360–796 m 2 /g). The gas permeation properties of SFX-PIM-25 and SFX-PIM-33 were evaluated and they exhibited high gas permeability (CO 2  = 3595–4034 Barrer). The gas permeability data of SFX-PIM-25 and SFX-PIM-33 was located close to 1991 Robson upper bound for CO 2 /N 2 , CO 2 /CH 4 and O 2 /N 2 gas pairs.