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The mechanochemical Friedel-Crafts polymerization as a solvent-free cross-linking approach toward microporous polymers

Krusenbaum, A. and Geisler, J. and Kraus, F.J.L. and Grätz, S. and Höfler, M.V. and Gutmann, T. and Borchardt, L.

JOURNAL OF POLYMER SCIENCE
Volume: 60 Pages: 62-71
DOI: 10.1002/pol.20210606
Published: 2022

Abstract
Herein we report the mechanochemical Friedel-Crafts alkylation of 1,3,5-triphenylbenzene (TPB) with two organochloride cross-linking agents, dichloromethane (DCM) and chloroform (CHCl3), respectively. During a thorough milling parameter evaluation, the DCM-linked polymers were found to be flexible and extremely sensitive toward parameter changes, which even enables the synthesis of a polymer with a SSABET of 1670 m2/g, on par with the solution-based reference. Contrary, CHCl3-linked polymers are exhibiting a rigid structure, with a high porosity that is widely unaffected by parameter changes. As a result, a polymer with a SSABET of 1280 m2/g could be generated in as little as 30 minutes, outperforming the reported literature analogue in terms of synthesis time and SSABET. To underline the environmental benefits of our fast and solvent-free synthesis approach, the green metrics are discussed, revealing an enhancement of the mass intensity, mass productivity and the E-factor, as well as of synthesis time and the work-up in comparison to the classical synthesis. Therefore, the mechanochemical polymerization is presented as a versatile tool, enabling the generation of highly porous polymers within short reaction times, with a minimal use of chlorinated cross-linker and with the possibility of a post polymerization modification. © 2021 The Authors. Journal of Polymer Science published by Wiley Periodicals LLC.

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