Five-Minute Mechanosynthesis of Hypercrosslinked Microporous Polymers

Designable porous materials have potential in a plethora of applications, but synthesis costs and strict reaction conditions limit their true commercialization. Herein, we show that hypercrosslinked polymers (HCPs) can be synthesized within minutes in a green, low-cost, mechanochemical route which avoids the use of traditional toxic solvents. Microporous HCPs were obtained in as little as 10 s, with optimum surface areas up to 782 m(2) g(-1) obtained in only 5 min and in quantitative yields for both Friedel-Crafts knitting and Scholl-coupling (SC) reactions. Liquid-assisted grinding of the SC model system resulted in higher porosity than the traditional solution-synthesized equivalent. ssNMR studies showed that a higher degree of polymerization was obtained from mechanosynthesis with the presence of a trace green solvent as a porogen resulting in such high porosity. This method allows a near limitless variety of highly porous polymers to be synthesized from an aromatic molecule within minutes.