Mathematical Modeling of Sustainable Cu(0)-RDRP: Methyl Methacrylate in Cyrene® at Ambient Temperature

Precise control over polymer molecular architecture is critical for the development of advanced functional materials with tailored properties. Reversible Deactivation Radical Polymerization (RDRP) techniques enable the synthesis of well-defined polymers under mild and scalable conditions, making them highly suitable for industrial applications. Among these methods, Cu(0)-mediated polymerization stands out for its use of a reusable copper-wire catalyst, low transition-metal concentrations, and ambient temperature operation. These features significantly reduce purification costs, energy consumption, and environmental impact, aligning with the principles of green chemistry.

Notably, the polymerization of methyl methacrylate (MMA) proceeds efficiently in Cyrene®, a bio-based, non-toxic solvent derived from cellulose, making it a promising alternative to conventional organic solvents. High levels of monomer conversion and polydispersity indices below 1.5 were achieved under ambient conditions, confirming the system’s efficiency.

In this study, we investigated the Cu(0)-mediated polymerization of MMA in Cyrene®, focusing on the estimation of kinetic parameters based on experimental data generated in our laboratory. A mathematical model was developed using the well-established method of moments, allowing for simulation of the polymerization kinetics. The model showed strong agreement with experimental results, supporting its predictive capability.

This work contributes to the development of more sustainable polymer-manufacturing strategies and demonstrates the value of kinetic modeling as a tool for guiding the process optimization and industrial-scale implementation of green polymerization techniques.