RESUMEN
We introduce the first mechanochemical cyclotrimerization of nitriles, a facile strategy for synthesizing triazine-containing molecules and materials, overcoming challenges related to carbonization and solubility. Conducting this solid-state approach in a mixer ball mill with 4-Methylbenzonitrile, we synthesize Tris(4-methylphenyl)-1,3,5-triazine quantitatively in as little as 90â minutes. Just as fast, this mechanochemical method facilitates the synthesis of the covalent triazine framework CTF-1 using 1,4â Dicyanobenzene. Material characterization confirms its porous (650â m2 g-1) and crystalline nature. Adjusting the induced mechanical energy allows control over the obtained stacking conformation of the resulting CTFs - from a staggered AB arrangement to an eclipsed AA stacking conformation. Finally, a substrate scope demonstrates the versatility of this approach, successfully yielding various CTFs.
RESUMEN
Herein we report the mechanochemical Scholl polymerization of 1,3,5-triphenylbenzene in a high speed ball mill. The reaction is conducted solvent-free, solely using solid FeCl3. The resulting porous polymer was obtained in >99% yield after very short reaction times of only 5 minutes and exhibits a high specific surface area of 658 m2 g-1, which could be further enhanced up to 990 m2 g-1 by liquid assisted grinding. Within this study we illuminate the origin of porosity by investigating the impact of various milling parameters and milling materials, temperature and pressure, and different liquids for LAG as well as post polymer milling. Finally we expand the procedure to different monomers and mills, to present the mechanochemical Scholl reaction as a versatile synthesis tool for porous polymers.