Vapor-phase postsynthetic amination of hypercrosslinked polymers for efficient iodine capture

Hypercrosslinked polymers (HCPs) with large surface areas, high intrinsic porosities and low production costs may be available platforms for iodine capture. However, the lack of iodine-philicity binding sites limits their adsorption capacity. Here we use vapor-phase postsynthetic amination strategy to introduce electron-donating amino groups into the prefabricated HCPs for enhancing their iodine capture performance. Through simple vapor-phase exposure, the halogen-containing HCPs can be grafted by amines through nucleophilic substitution toward chloro groups. Combining with the abundant amino groups and high porosities, the amino-functionalized porous polymers show substantially increased iodine adsorption capacity, about 221% as that of original one, accompanied by excellent recyclability. Mechanism investigations reveal the key roles of the electron-donor amino groups and π-conjugated benzene rings along with structure characteristics of porous polymer frameworks in iodine capture. Moreover, this vapor-phase amination strategy shows good generality and can be extended to various amines, e.g., ethylenediamine, 1,3-diaminopropane and diethylenetriamine. Our work proves that this simple vapor-phase postsynthetic functionalization strategy may be applied in other porous polymers with wide application prospects in adsorption, separation and storage. Vapor-phase amination is used to graft halogen-based hypercrosslinked polymers with abundant electron-donor amino groups and high porosities, which show impressive iodine capture performances. [Display omitted]