Double neighbouring group participation for ultrafast exchange in phthalate monoester networks
- Author
- Maarten Delahaye, Flaminia Tanini, Joshua Holloway (UGent) , Johan Winne (UGent) and Filip Du Prez (UGent)
- Organization
- Abstract
- Phthalate monoesters (PMEs) were recently introduced as a simple dynamic covalent bond for implementation in covalent adaptable networks (CANs), which undergo rapid transesterifications in the absence of catalysts, due to the neighbouring group participation (NGP) of a carboxylic acid moiety. In this work, it is shown that the PME transesterification can be very significantly accelerated by the presence of another neighbouring group on the reactive alcohol moieties. The kinetic effects are demonstrated using a short model study of PMEs with different substituents at the β-carbon position, showing a remarkable acceleration for alcohols containing tertiary amines on the β-carbon. Following the model study, materials were synthesised by a (partial) replacement of the conventionally used diol with a β-amino-diol, leading to the formation of networks with an increased Tg and Young's-modulus, which is rationalised as a result of the formation of an ionic network (COO− and NHR3+). Stress relaxation experiments show a decrease in relaxation times by a factor of 500, compared to similar networks derived from non-amine-substituted hydroxyl monomers. This ultrafast relaxation, enabled by a double NGP, resulted in CANs that show potential to be processed through extrusion while maintaining their overall network connectivity.
- Keywords
- Organic Chemistry, Biochemistry, Bioengineering, Polymers and Plastics, VITRIMERS, CHEMISTRY
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Citation
Please use this url to cite or link to this publication: http://hdl.handle.net/1854/LU-8675914
- MLA
- Delahaye, Maarten, et al. “Double Neighbouring Group Participation for Ultrafast Exchange in Phthalate Monoester Networks.” POLYMER CHEMISTRY, vol. 11, no. 32, 2020, pp. 5207–15, doi:10.1039/d0py00681e.
- APA
- Delahaye, M., Tanini, F., Holloway, J., Winne, J., & Du Prez, F. (2020). Double neighbouring group participation for ultrafast exchange in phthalate monoester networks. POLYMER CHEMISTRY, 11(32), 5207–5215. https://doi.org/10.1039/d0py00681e
- Chicago author-date
- Delahaye, Maarten, Flaminia Tanini, Joshua Holloway, Johan Winne, and Filip Du Prez. 2020. “Double Neighbouring Group Participation for Ultrafast Exchange in Phthalate Monoester Networks.” POLYMER CHEMISTRY 11 (32): 5207–15. https://doi.org/10.1039/d0py00681e.
- Chicago author-date (all authors)
- Delahaye, Maarten, Flaminia Tanini, Joshua Holloway, Johan Winne, and Filip Du Prez. 2020. “Double Neighbouring Group Participation for Ultrafast Exchange in Phthalate Monoester Networks.” POLYMER CHEMISTRY 11 (32): 5207–5215. doi:10.1039/d0py00681e.
- Vancouver
- 1.Delahaye M, Tanini F, Holloway J, Winne J, Du Prez F. Double neighbouring group participation for ultrafast exchange in phthalate monoester networks. POLYMER CHEMISTRY. 2020;11(32):5207–15.
- IEEE
- [1]M. Delahaye, F. Tanini, J. Holloway, J. Winne, and F. Du Prez, “Double neighbouring group participation for ultrafast exchange in phthalate monoester networks,” POLYMER CHEMISTRY, vol. 11, no. 32, pp. 5207–5215, 2020.
@article{8675914, abstract = {{Phthalate monoesters (PMEs) were recently introduced as a simple dynamic covalent bond for implementation in covalent adaptable networks (CANs), which undergo rapid transesterifications in the absence of catalysts, due to the neighbouring group participation (NGP) of a carboxylic acid moiety. In this work, it is shown that the PME transesterification can be very significantly accelerated by the presence of another neighbouring group on the reactive alcohol moieties. The kinetic effects are demonstrated using a short model study of PMEs with different substituents at the β-carbon position, showing a remarkable acceleration for alcohols containing tertiary amines on the β-carbon. Following the model study, materials were synthesised by a (partial) replacement of the conventionally used diol with a β-amino-diol, leading to the formation of networks with an increased Tg and Young's-modulus, which is rationalised as a result of the formation of an ionic network (COO− and NHR3+). Stress relaxation experiments show a decrease in relaxation times by a factor of 500, compared to similar networks derived from non-amine-substituted hydroxyl monomers. This ultrafast relaxation, enabled by a double NGP, resulted in CANs that show potential to be processed through extrusion while maintaining their overall network connectivity.}}, author = {{Delahaye, Maarten and Tanini, Flaminia and Holloway, Joshua and Winne, Johan and Du Prez, Filip}}, issn = {{1759-9954}}, journal = {{POLYMER CHEMISTRY}}, keywords = {{Organic Chemistry,Biochemistry,Bioengineering,Polymers and Plastics,VITRIMERS,CHEMISTRY}}, language = {{eng}}, number = {{32}}, pages = {{5207--5215}}, title = {{Double neighbouring group participation for ultrafast exchange in phthalate monoester networks}}, url = {{http://doi.org/10.1039/d0py00681e}}, volume = {{11}}, year = {{2020}}, }
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