Lee, Z. Y., Kamarulzaman, S., Rasyiddin, R., Sim, S. Y. X., Seah, G. E. K. K., Gan, A. W., Li, Z., Png, Z. M., & Goh, S. S. (2025). Dynamic crosslinking of thermoplastics via perfluorophenyl nitrene C–H insertion to form recyclable thermosets. Chem, 102479. https://doi.org/10.1016/j.chempr.2025.102479
Abstract:
Covalent adaptable networks (CANs) are polymers crosslinked via dynamic covalent bonds (DCBs), endowing the networks with both thermoset-like stability and thermoplastic-like recyclability. Although post-polymerization crosslinking of thermoplastics is an efficient strategy to form CANs, the process is non-trivial, especially for poly(olefins) that have low functionality and a fully hydrocarbon backbone. Herein, we introduce perflurophenyl azide-based nitrene crosslinkers to install disulfide, imine, and acetal DCBs into poly(olefins) and other thermoplastics, thereby converting them into CANs. Crosslinking was effective for a wide range of thermoplastics, imparting both dimensional and solvent stability. The resultant CANs could also exhibit enhanced mechanical performance, such as doubling of tensile toughness and self-healing ability. Unlike traditional thermosets, the DCBs enabled these CANs to be chemically and/or mechanically recycled multiple times. This methodology has the advantage of utilizing existing and even post-consumer plastic blends as starting materials, improving their thermo-mechanical properties while maintaining recyclability of the synthesized CANs.
License type:
Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)
Funding Info:
This research / project is supported by the Agency for Science, Technology and Research - Manufacturing, Trade and Connectivity (MTC) Programmatic Fund
Grant Reference no. : M22K9b0049
Description:
For the publisher's version, refer here: https://doi.org/10.1016/j.chempr.2025.102479