Toward Recyclable Polymers: Ring-Opening Polymerization Enthalpy from First-Principles

Ring-opening polymerization (ROP) enthalpy Delta H-ROP is an important thermodynamic property controlling the polymerization of cyclic monomers. While Delta H-ROP can be measured, computing Delta H-ROP for realistic polymer systems with an error of similar or equal to 5-10 kJ/mol is critical for designing new monomer systems for depolymerizable polymers. We have developed a first-principles computational scheme in which multiple challenges in computing Delta H-ROP are resolved definitively including extensive exploration of conformational states and adequately addressing finite size effects. This scheme is validated on a diverse benchmark set of 42 ROP polymers for which reliable experimental values of Delta H-ROP are available. For this set, the Delta H-ROP root-mean-square error is similar or equal to 7 kJ/mol, about 3-times smaller than conventional approaches. This development opens up new pathways to build up a high-quality database of Delta H-ROP for downstream predictive machine-learning models and ultimately to accelerate the design of depolymerizable polymers with desired properties.

Automated summary

This study developed a first-principles computational scheme for accurately calculating the enthalpy of ring-opening polymerization (Delta H-ROP). The scheme demonstrated a smaller root-mean-square error compared to conventional approaches when validated on a diverse benchmark set. This development opens up new pathways for building a high-quality database of Delta H-ROP and accelerating the design of depolymerizable polymers.