Cited by 334Polymer composites and self-healingEpoxy Resin Curing ProcessesHydrogels: synthesis, properties, applications

Internal Catalysis in Covalent Adaptable Networks: Phthalate Monoester Transesterification As a Versatile Dynamic Cross-Linking Chemistry

Delahaye, Maarten, Winne, Johan M., Du Prez, Filip E.·2019·Journal of the American Chemical Society

Abstract

Covalent adaptable networks (CANs) often make use of highly active external catalysts to provide swift exchange of the dynamic chemical bonds. Alternatively, milder species can act as internal catalysts when covalently attached to the matrix and in close proximity to the dynamic bonds. In this context, we introduce the dynamic exchange of phthalate monoesters as a novel chemistry platform for covalent adaptable networks. A low-molecular-weight (MW) model study shows that these monoesters undergo fast transesterification via a dissociative mechanism, caused by internal catalysis of the free carboxylic acid, which reversibly forms an activated phthalic anhydride intermediate. Using this dynamic chemistry, a wide series of CANs with a broad range of properties have been prepared by simply curing a mixture of diols and triols with bifunctional phthalic anhydrides. The dynamic nature of the networks was confirmed via recycling experiments for multiple cycles and via stress relaxation using rheology. The networks proved to be resistant to deformation but showed a marked temperature response in their rheological behavior, related to the swift exchange reactions that have a high activation energy (120 kJ/mol). While densely cross-linked and hydrolytically stable polyester networks with low soluble fractions can be obtained, we found that, by swelling the networks in a hot solvent, a gel-to-sol transition happened, which resulted in the full dissolution of the network.

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Crossref · 10.1021/jacs.9b07269

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Authors
Delahaye, M., Winne, J. M., & Du Prez, F. E.
Affiliations
  • Ghent University (BE)
  • Polymer Chemistry Research Group (PCR), Centre of Macromolecular Chemistry (CMaC), Department of Organic and Macromolecular Chemistry, Ghent University, Krijgslaan 281 S4-bis, B-9000 Ghent, Belgium
Corresponding author
Winne, Johan M.
Venue
Journal of the American Chemical Society
Published
2019-08-30
Volume
141
Issue
38
Pages
15277-15287
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
OpenAlex
W2970155847
Cited by
334
References
62
Citations by year
2026: 34 · 2025: 64 · 2024: 72 · 2023: 54 · 2022: 48 · 2021: 29 · 2020: 30 · 2019: 3
FWCI
11.74
Type
journal article
Language
en
Open access
closed
Locations
  • Journal of the American Chemical Society (publishedVersion)
  • PubMed (publishedVersion)
  • Ghent University Academic Bibliography (Ghent University) (submittedVersion)
Funders
  • Universiteit Gent
  • Fonds Wetenschappelijk Onderzoek
  • Bijzonder Onderzoeksfonds
Topics
  • Physical Sciences › Materials Science › Polymers and Plastics › Polymer composites and self-healing
  • Physical Sciences › Engineering › Mechanical Engineering › Epoxy Resin Curing Processes
  • Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Medicine › Hydrogels: synthesis, properties, applications
Keywords
covalent adaptable networks, phthalate monoesters, transesterification, dynamic crosslinking, phthalic anhydride, dissociative mechanism, carboxylic acid activation, gel-sol transition, stress relaxation, hydrolytic stability

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