Compressible and monolithic microporous polymers (MPs) are reported. MPs were prepared as monoliths via a Sonogashira–Hagihara coupling reaction of 1,3,5-triethynylbenzene (TEB) with the bis(bromothiophene) monomer (PBT-Br). The polymers were reversibly compressible, and were easily cut into any form using a knife. Microscopy studies on the MPs revealed that the polymers had tubular microstructures, resembling those often found in marine sponges. Under compression, elastic buckling of the tube bundles was observed using an optical microscope. MP-0.8, which was synthesized using a 0.8:1 molar ratio of PBT-Br to TEB, showed microporosity with a BET surface area as high as 463 m2g–1. The polymer was very hydrophobic, with a water contact angle of 145° and absorbed 7–17 times its own weight of organic liquids. The absorbates were released by simple compression, allowing recyclable use of the polymer. MPs are potential precursors of structured carbon materials; for example, a partially graphitic material was obtained by pyrolysis of MP-0.8, which showed a similar tubular structure to that of MP-0.8.
Two constitutional isomers of a C3-symmetric molecule having cyano-vinylene bridges and a phenyl ring core show different piezochromic behaviours, on–off switching and colour tuning upon grinding.
A flexible microporous polymer paper (MPP) is prepared with the polymer tubes obtained from the Sonogashira coupling reaction of 1,4‐diiodotetrafluorobenzene and 1,3,5‐triethynylbenzene. MPP has an interconnected network structure of polymer tubes and shows a hierarchical pore structure. Relatively large pores are formed among entangled polymer tubes, while micro‐ and mesopores are generated in the tube walls. MPP is foldable, mechanically stable, and stretchable. When the folding stress is removed, a wrinkle forms along the folded line, as observed in common papers composed of cellulose pulps. The mechanical stability of MPP results from electrostatic interactions between electron deficient tetrafluorobenzene units and electron rich triethynylbenzene units in the polymer. The tensile stress–tensile strain curve shows that MPP can elongate up to 15% strain. MPP is superhydrophobic, showing a water contact angle of 162° and can be used for the filtration of small molecules such as a dye and iodine.
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