Abstract
The rapid advancement of dynamic covalent chemistry (DCvC) has significantly impacted both chemistry and materials science. There is an increasing need for exploring catalyst-free dynamic covalent reactions with large equilibrium con-stant (Keq) ranges to provide new avenues for the tailored design of dynamers. Here, we report a catalyst-free dynamic covalent condensation reaction between Knoevenagel derivatives and hydrazides to generate acylhydrazones. Systematic small-molecule studies validate a significant substituent effect on the Kn reactant, resulting in a wide Keq range covering nearly four orders of magnitude (0.1 ~ 719). The high Keq values (> 500) achieved in polar aprotic solvents enable the catalyst-free synthesis of high-molar-mass (~ 180 kDa) polyacylhydrazones. The retention of by-products during poly-condensation leads to concentration-dependent topology switching between polymeric and macrocyclic acylhydrazones. By leveraging this reaction, we developed a novel covalent adaptable network (CAN) that exhibits remarkable stress re-laxation properties (38 s at 160 °C), facilitating efficient thermal reprocessing while maintaining high mechanical perfor-mance. This condensation reaction enriches the dynamic covalent toolbox and offers a versatile approach for the design and fabrication of dynamers with tailored mechanical and dynamic behavior.
Supplementary materials
Title
Catalyst-free Dynamic Covalent Knoevenagel/Hydrazide Condensa-tion for Polyacylhydrazones and Covalent Adaptable Networks
Description
we report a catalyst-free dynamic covalent condensation reaction between Knoevenagel derivatives and hydrazides to generate acylhydrazones. Systematic small-molecule studies validate a significant substituent effect on the Kn reactant, resulting in a wide Keq range covering nearly four orders of magnitude (0.1 ~ 719). The high Keq values (> 500) achieved in polar aprotic solvents enable the catalyst-free synthesis of high-molar-mass (~ 180 kDa) polyacylhydrazones. The retention of by-products during poly-condensation leads to concentration-dependent topology switching between polymeric and macrocyclic acylhydrazones. By leveraging this reaction, we developed a novel covalent adaptable network (CAN) that exhibits remarkable stress re-laxation properties (38 s at 160 °C), facilitating efficient thermal reprocessing while maintaining high mechanical perfor-mance. This condensation reaction enriches the dynamic covalent toolbox and offers a versatile approach for the design and fabrication of dynamers with tailored mechanical and dynamic behavior.
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