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Covalent adaptable networks using boronate linkages by incorporating TetraAzaADamantanes

Boronic esters prepared by condensation of boronic acids and diols have been widely used as dynamic covalent bonds in the synthesis of both discrete assemblies and polymer networks. In this study we investigate the potential of a new dynamic-covalent motif, derived from TetraAzaADamantanes (TAADs),...

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Autores principales: van Hurne, Simon, Kisters, Marijn, Smulders, Maarten M. J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Frontiers Media S.A. 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9995436/
https://www.ncbi.nlm.nih.gov/pubmed/36909710
http://dx.doi.org/10.3389/fchem.2023.1148629
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author van Hurne, Simon
Kisters, Marijn
Smulders, Maarten M. J.
author_facet van Hurne, Simon
Kisters, Marijn
Smulders, Maarten M. J.
author_sort van Hurne, Simon
collection PubMed
description Boronic esters prepared by condensation of boronic acids and diols have been widely used as dynamic covalent bonds in the synthesis of both discrete assemblies and polymer networks. In this study we investigate the potential of a new dynamic-covalent motif, derived from TetraAzaADamantanes (TAADs), with their adamantane-like triol structure, in boronic ester-based covalent adaptable networks (CANs). The TetraAzaADamantane-boronic ester linkage has recently been reported as a more hydrolytically stable boronic ester variant, while still having a dynamic pH response: small-molecule studies found little exchange at neutral pH, while fast exchange occurred at pH 3.8. In this work, bi- and trifunctional TetraAzaADamantane linkers were synthesised and crosslinked with boronic acids to form rubber-like materials, with a Young’s modulus of 1.75 MPa. The dynamic nature of the TetraAzaADamantane networks was confirmed by stress relaxation experiments, revealing Arrhenius-like behaviour, with a corresponding activation energy of 142 ± 10 kJ/mol. Increasing the crosslinking density of the material from 10% to 33% resulted in reduced relaxation times, as is consistent with a higher degree of crosslinking within the dynamic networks. In contrast to the reported accelerating effect of acid addition to small-molecule TetraAzaADamantane complexes, within the polymer network the addition of acid increased relaxation times, suggesting unanticipated interactions between the acid and the polymer that cannot occur in the corresponding small-molecules analogues. The obtained boronate-TetraAzaADamantane materials were thermally stable up to 150°C. This thermal stability, in combination with the intrinsically dynamic bonds inside the polymer network, allowed these materials to be reprocessed and healed after damage by hot-pressing.
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spelling pubmed-99954362023-03-10 Covalent adaptable networks using boronate linkages by incorporating TetraAzaADamantanes van Hurne, Simon Kisters, Marijn Smulders, Maarten M. J. Front Chem Chemistry Boronic esters prepared by condensation of boronic acids and diols have been widely used as dynamic covalent bonds in the synthesis of both discrete assemblies and polymer networks. In this study we investigate the potential of a new dynamic-covalent motif, derived from TetraAzaADamantanes (TAADs), with their adamantane-like triol structure, in boronic ester-based covalent adaptable networks (CANs). The TetraAzaADamantane-boronic ester linkage has recently been reported as a more hydrolytically stable boronic ester variant, while still having a dynamic pH response: small-molecule studies found little exchange at neutral pH, while fast exchange occurred at pH 3.8. In this work, bi- and trifunctional TetraAzaADamantane linkers were synthesised and crosslinked with boronic acids to form rubber-like materials, with a Young’s modulus of 1.75 MPa. The dynamic nature of the TetraAzaADamantane networks was confirmed by stress relaxation experiments, revealing Arrhenius-like behaviour, with a corresponding activation energy of 142 ± 10 kJ/mol. Increasing the crosslinking density of the material from 10% to 33% resulted in reduced relaxation times, as is consistent with a higher degree of crosslinking within the dynamic networks. In contrast to the reported accelerating effect of acid addition to small-molecule TetraAzaADamantane complexes, within the polymer network the addition of acid increased relaxation times, suggesting unanticipated interactions between the acid and the polymer that cannot occur in the corresponding small-molecules analogues. The obtained boronate-TetraAzaADamantane materials were thermally stable up to 150°C. This thermal stability, in combination with the intrinsically dynamic bonds inside the polymer network, allowed these materials to be reprocessed and healed after damage by hot-pressing. Frontiers Media S.A. 2023-02-23 /pmc/articles/PMC9995436/ /pubmed/36909710 http://dx.doi.org/10.3389/fchem.2023.1148629 Text en Copyright © 2023 van Hurne, Kisters and Smulders. https://creativecommons.org/licenses/by/4.0/This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
spellingShingle Chemistry
van Hurne, Simon
Kisters, Marijn
Smulders, Maarten M. J.
Covalent adaptable networks using boronate linkages by incorporating TetraAzaADamantanes
title Covalent adaptable networks using boronate linkages by incorporating TetraAzaADamantanes
title_full Covalent adaptable networks using boronate linkages by incorporating TetraAzaADamantanes
title_fullStr Covalent adaptable networks using boronate linkages by incorporating TetraAzaADamantanes
title_full_unstemmed Covalent adaptable networks using boronate linkages by incorporating TetraAzaADamantanes
title_short Covalent adaptable networks using boronate linkages by incorporating TetraAzaADamantanes
title_sort covalent adaptable networks using boronate linkages by incorporating tetraazaadamantanes
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9995436/
https://www.ncbi.nlm.nih.gov/pubmed/36909710
http://dx.doi.org/10.3389/fchem.2023.1148629
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