Solid-state polycyclotrimerization of diynes to porous organic polymers

Herein, we report a solid-state polycyclotrimerization of 1,4-diethynylbenzene using mechanochemical activation in a ball mill, yielding a highly porous and hydrophobic hyperbranched polymer (HBP) with a specific surface area of up to 570 m² g^-1. The reaction, catalyzed by Fe(hmds)₂ and conducted under solvent-free conditions, was optimized by varying milling time and frequency. This method enables the efficient synthesis of insoluble, porous organic polymers with high yields (up to 95%) and offers an environmentally friendly alternative to traditional solution-based polymerizations.