[en] New dynamic chemistry is nowadays sought to widen the library of accessible covalent adaptable networks (CANs). Here, we investigate the dynamic nature of CO2-sourced cyclic S,O-acetal bonds under unexplored conditions. Model molecule studies were conducted on various compounds and supported by extensive DFT calculations to understand the required conditions for triggering exchange and the underlying reaction mechanisms. This is the first study to report dynamic S,O-acetal bonds with an unprecedented associative exchange mechanism occurring through nucleophilic attack onto a remote function from the exchanged site. Our findings were translated to macromolecular engineering with the successful production of CO2-sourced CANs embedding cyclic S,O-acetal bonds from bifunctional alkylidene cyclic carbonates and polythiols. The polymer properties were tuned by the use of structurally divergent monomers, affording materials with distinct thermal and mechanical properties (e.g. Tg ranging from 2 to 51 °C). Complex relaxation behaviour was recorded by rheology experiments, suggesting concurrent exchange reactions to take place at elevated temperatures. The materials dynamics was leveraged through recycling by compression molding for over five cycles. Furthermore, a proof-of-concept coating application was developed, showcasing damage healing at high temperatures.
Research Center/Unit :
CESAM - Complex and Entangled Systems from Atoms to Materials - ULiège CERM - Center for Education and Research on Macromolecules - ULiège
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Maes, Stephan ✱; University of Gent [UGent] - Centre of Macromolecular Chemistry - Polymer Chemistry Research Group - Belgium
Habets, Thomas ✱; University of Liège [ULiège] - Complex and Entangled Systems from Atoms to Materials [CESAM] Research Unit - Center for Education and Research on Macromolecules [CERM] - Belgium
Fischer, Susanne M. ; University of Gent [UGent] - Centre of Macromolecular Chemistry - Polymer Chemistry Research Group - Belgium
Grignard, Bruno ; University of Liège [ULiège] - Complex and Entangled Systems from Atoms to Materials [CESAM] Research Unit - Center for Education and Research on Macromolecules [CERM] - Belgium ; University of Liège [ULiège] - FRITCO2T Platform - Belgium
Detrembleur, Christophe ✱; University of Liège [ULiège] - Complex and Entangled Systems from Atoms to Materials [CESAM] Research Unit - Center for Education and Research on Macromolecules [CERM] - Belgium
Du Prez, Filip E. ✱; University of Gent [UGent] - Centre of Macromolecular Chemistry - Polymer Chemistry Research Group - Belgium
✱ These authors have contributed equally to this work.
Language :
English
Title :
Unprecedented associative exchange in CO2-sourced cyclic S,O-acetal-based covalent adaptable networks
Publication date :
10 May 2024
Journal title :
Polymer Chemistry
ISSN :
1759-9954
eISSN :
1759-9962
Publisher :
Royal Society of Chemistry
Volume :
15
Issue :
22
Pages :
2296 - 2307
Peer reviewed :
Peer Reviewed verified by ORBi
Tags :
CÉCI : Consortium des Équipements de Calcul Intensif
Funders :
FWO - Flemish Research Foundation F.R.S.-FNRS - Fonds de la Recherche Scientifique Flemish Supercomputer Center
Funding text :
S. M. acknowledges Ghent University for funding of his doctoral research (DOCT/009009). The authors from the University of Li\u00E8ge thank FNRS for the financial support in the frame of the CO Switch project under grant T.0075.20. C. D. is a F.R.S.-FNRS Research Director. Computational resources have been provided by the Consortium des \u00C9quipements de Calcul Intensif (C\u00C9CI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under grant no. 2.5020.11 and by the Walloon Region. Computational resources (Stevin Supercomputer Infrastructure) and services used in this work were provided by the VSC (Flemish Supercomputer Center), funded by Ghent University, FWO and the Flemish Government- department EWI. The NMR expertise centre (Ghent University) is also acknowledged for providing support and access to NMR infrastructure. 400 MHz used in this work has been funded by a grant/project of the Research Foundation Flanders (FWO I006920N) and the Bijzonder Onderzoeksfonds (BOF.BAS.2022.0023.01). Bernhard De Meyer and Jan Goeman are acknowledged for technical support. Vincent Scholiers is acknowledged for his help during the synthesis of the TVC-trithiol.
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