Structure, Dynamics, and Rheology of Vitrimers

JS Xia and JA Kalow and MO de la Cruz, MACROMOLECULES, 56, 8080-8093 (2023).

DOI: 10.1021/acs.macromol.3c01366

Vitrimers are associative covalent adaptable networks that undergo reversible bond-exchange reactions while maintaining a fixed cross- linking density with changing temperature. To date, experimental studies that rely on macroscopic rheology have not been able to reveal topological changes and microscopic dynamics in these materials. Here, coarse-grained molecular dynamics simulations combined with a Monte Carlo method are implemented to investigate the topological structural changes, microscopic dynamics, and linear rheology of unentangled side- chain-linked vitrimers in conjunction with the sticky Rouse model (SRM). We find that there is a minor variation in the topological structure with temperature. The dynamic heterogeneities of the bond-exchange behavior and the system dynamics increase remarkably when approaching the topological freezing transition temperature T-v . Quantitative agreement between the simulation results and the SRM predictions is observed for the stress relaxation, elastic and loss moduli, and the relative mean-squared displacement, especially at the intermediate- and long-time or low-frequency regimes, where the time-temperature superposition principle is satisfied. We obtain a scaling collapse curve for the dynamic bond relaxation time, the zero-shear viscosity, and the horizontal shift factors without introducing any parameters, suggesting that the microscopic and macroscopic dynamics exhibit a similar relaxation behavior even in the presence of loop defects. Moreover, these results are in good agreement with those predicted by the SRM, indicating that the linear rheology of unentangled vitrimers with a fast bond-exchange rate can be analyzed via a single-chain approach based on the SRM.

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