A hybrid in-silico and experimental kinetics study of glycidyl methacrylate-functionalized N-vinylcaprolactam microgel synthesis

The synthesis of microgels with new functionalities is vital for a variety of applications, e.g., in drug release systems[1] and enzyme immobilization[2]; however, the synthesis kinetics of microgels remain largely unknown. In this contribution, we study the synthesis of glycidyl methacrylate-functionalized N-vinylcaprolactam-based microgels. A hybrid approach using quantum chemical calculations and experimental data allows us to estimate parameter values for unknown reaction rates in the existing synthesis model[3]. Using quantum mechanics, we compute gas-phase propagation rate constants and enthalpies of the underlying polymerization reactions at B2PLYPD3/aug-cc-pVTZ and B3LYPD3/tzvp level of theory for the energies and geometries, respectively. Solvation effects based on COSMO-RS are incorporated to obtain liquid-phase reaction rate constants and enthalpies. Using reaction calorimetry measurements and the mechanistic process model, we estimate seven out of twenty-one reaction parameters. As a result of our hybrid approach, we find a coefficient of determination of 0.97 for the enthalpy transfer rate during microgel synthesis. In the future, the fully identified model will help determine the optimal pVCL/GMA microgel synthesis conditions.

References

[1] P. Li et al., Coll. & Surf. B: Biointerfaces 101, 251–255, 2013.

[2] D. Rommel et al., Adv. Sci. 9(10), 2103554, 2022.

[3] S. Schneider et al., Polym. Chem. 11, 315–325, 2020.