Accelerated Post-Polymerization Amidation of Polymers with Side-Chain Ester Groups by Intramolecular Activation

Title data

Van Guyse, Joachim F. R. ; Leiske, Meike N. ; Verjans, Jente ; Bernhard, Yann ; Hoogenboom, Richard:
Accelerated Post-Polymerization Amidation of Polymers with Side-Chain Ester Groups by Intramolecular Activation.
In: Angewandte Chemie International Edition. Vol. 61 (2022) Issue 29 . - e202201781.
ISSN 1521-3773
DOI: https://doi.org/10.1002/anie.202201781

Official URL:

Abstract in another language

The catalytic conversion of esters to amides represents new opportunities in the synthetic diversification and upcycling of polymers, as esters are commonly featured in various polymer structures. Yet, direct amidation is typically hampered by poor reaction kinetics and the effects of polymer structure on the reactivity remain poorly understood. We report the accelerated amidation for amines with additional hydrogen bond donating or accepting groups. These amines facilitate the expeditious (co)amidation of polymers with pendant ester groups, displaying at least a 400-fold higher reactivity relative to polyesters with esters in the main chain. Furthermore, a positive correlation between the reactivity and degree of polymerization for poly(methyl acrylate) suggests a hydrogen-bond mediated intramolecular activation of the esters, which was confirmed by FT-IR spectroscopy and basic molecular mechanics modeling. The reported method paves the way to synthesize diverse (co)polymers with amide side chains from readily available polymeric precursors.

Further data

Item Type:	Article in a journal
Refereed:	Yes
Keywords:	Amines; Catalysis; Esters; Polymers; Post-Polymerization Modification
Institutions of the University:	Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry Faculties Faculties > Faculty of Biology, Chemistry and Earth Sciences Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Junior Professor Sustainable and Functional Polymer Systems > Junior Professor Sustainable and Functional Polymer Systems - Juniorprof. Dr. Meike Leiske Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Junior Professor Sustainable and Functional Polymer Systems
Result of work at the UBT:	No
DDC Subjects:	500 Science > 540 Chemistry
Date Deposited:	18 Jan 2023 14:45
Last Modified:	13 Mar 2023 08:44
URI:	https://eref.uni-bayreuth.de/id/eprint/73451