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Internal catalysis in covalent adaptable networks : phthalate monoester transesterification as a versatile dynamic cross-linking chemistry

Maarten Delahaye (UGent) , Johan Winne (UGent) and Filip Du Prez (UGent)
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Organization
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.
Keywords
RING-OPENING POLYMERIZATION, NEIGHBORING GROUP PARTICIPATION, CONTROLLED ACTIVITY POLYMERS, HYDROLYSIS, ESTER, VITRIMER, EXCHANGE, RELEASE, POLYURETHANE, COPOLYMERS

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MLA
Delahaye, Maarten, et al. “Internal Catalysis in Covalent Adaptable Networks : Phthalate Monoester Transesterification as a Versatile Dynamic Cross-Linking Chemistry.” JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 141, no. 38, 2019, pp. 15277–87.
APA
Delahaye, M., Winne, J., & Du Prez, F. (2019). Internal catalysis in covalent adaptable networks : phthalate monoester transesterification as a versatile dynamic cross-linking chemistry. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 141(38), 15277–15287.
Chicago author-date
Delahaye, Maarten, Johan Winne, and Filip Du Prez. 2019. “Internal Catalysis in Covalent Adaptable Networks : Phthalate Monoester Transesterification as a Versatile Dynamic Cross-Linking Chemistry.” JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 141 (38): 15277–87.
Chicago author-date (all authors)
Delahaye, Maarten, Johan Winne, and Filip Du Prez. 2019. “Internal Catalysis in Covalent Adaptable Networks : Phthalate Monoester Transesterification as a Versatile Dynamic Cross-Linking Chemistry.” JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 141 (38): 15277–15287.
Vancouver
1.
Delahaye M, Winne J, Du Prez F. Internal catalysis in covalent adaptable networks : phthalate monoester transesterification as a versatile dynamic cross-linking chemistry. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. 2019;141(38):15277–87.
IEEE
[1]
M. Delahaye, J. Winne, and F. Du Prez, “Internal catalysis in covalent adaptable networks : phthalate monoester transesterification as a versatile dynamic cross-linking chemistry,” JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 141, no. 38, pp. 15277–15287, 2019.
@article{8634575,
  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.},
  author       = {Delahaye, Maarten and Winne, Johan and Du Prez, Filip},
  issn         = {0002-7863},
  journal      = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY},
  keywords     = {RING-OPENING POLYMERIZATION,NEIGHBORING GROUP PARTICIPATION,CONTROLLED ACTIVITY POLYMERS,HYDROLYSIS,ESTER,VITRIMER,EXCHANGE,RELEASE,POLYURETHANE,COPOLYMERS},
  language     = {eng},
  number       = {38},
  pages        = {15277--15287},
  title        = {Internal catalysis in covalent adaptable networks : phthalate monoester transesterification as a versatile dynamic cross-linking chemistry},
  url          = {http://dx.doi.org/10.1021/jacs.9b07269},
  volume       = {141},
  year         = {2019},
}

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