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Nitrogen Enriched Trgers Base Polymers of Intrinsic Microporosity (TB-PIMs) for Heterogeneous Catalysis

Tash Hawkins, Ariana Antonangelo, MITCHELL WOOD, Elena Tocci, Johannes Carolus Jansen Orcid Logo, Alessio Fuoco Orcid Logo, Carmen Rizzuto, Mariagiulia Longo, Caterina Bezzu Orcid Logo, Mariolino Carta Orcid Logo

ACS Applied Polymer Materials, Volume: 7, Issue: 1, Pages: 220 - 233

Swansea University Authors: Tash Hawkins, Ariana Antonangelo, MITCHELL WOOD, Caterina Bezzu Orcid Logo, Mariolino Carta Orcid Logo

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DOI (Published version): 10.1021/acsapm.4c02952

Abstract

Heterogeneous catalysis is significantly enhanced by the use of highly porous polymers with specific functionalities, such as basic groups, which accelerate reaction rates. Polymers of intrinsic microporosity (PIMs) provide a unique platform for catalytic reactions owing to their high surface areas...

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Published in: ACS Applied Polymer Materials
ISSN: 2637-6105
Published: American Chemical Society (ACS) 2025
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URI: https://cronfa.swan.ac.uk/Record/cronfa68476
Abstract: Heterogeneous catalysis is significantly enhanced by the use of highly porous polymers with specific functionalities, such as basic groups, which accelerate reaction rates. Polymers of intrinsic microporosity (PIMs) provide a unique platform for catalytic reactions owing to their high surface areas and customizable pore structures. We herein report a series of Tröger’s base polymers (TB-PIMs) with enhanced basicity, achieved through the incorporation of nitrogen-containing groups into their repeat units, such as triazine and triphenylamine. These polymers offer a perfect balance between the pore “swellability”, which allows the use of substrates of various dimensions, and the basicity of their repeat units, which facilitates the use of reactants with diverse acidity. The catalytic activity is evaluated through the Knoevenagel condensation of benzaldehydes and various methylene species, conducted in the presence of ethanol as a green solvent and using a 1:1 ratio of the two reagents. The results highlight a significant improvement, with reactions reaching completion using just a 1% molar ratio of catalysts and achieving a 3-fold enhancement over previous results with 4-tert-butyl-benzaldehyde. Computational modeling confirms that the enhanced basicity of the repeat units is attributable to the polymer design. Additionally, preliminary studies are undertaken to assess the kinetics of the catalyzed condensation reaction.
Keywords: Heterogeneous catalysis; Tröger’s base; PIMs; Knoevenagel; microporosity
College: Faculty of Science and Engineering
Funders: M.C., A.R.A., and N.H. gratefully acknowledge funding from the Engineering and Physical Sciences Research Council (EPSRC), Grant number: EP/T007362/1 “Novel polymers of intrinsic microporosity for heterogeneous base-catalysed reactions (HBC-PIMs)” and Swansea University. The authors kindly acknowledge Daniel M. Dawson and the University of St Andrews for the 13C SSNMR service. E.T., J.C.J., and A.F. received funding from the European Union’s Horizon Europe research and innovation program under grant agreement no. 101115488, within the EIC pathfinder project “DAM4CO2”. M.C., E.T., J.C.J., A.F., and C.G.B. also thank the Royal Society for the bilateral grant IEC\R2\222044.
Issue: 1
Start Page: 220
End Page: 233