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

H Tran and A Toland and K Stellmach and MK Paul and W Gutekunst and R Ramprasad, JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 4778-4785 (2022).

DOI: 10.1021/acs.jpclett.2c00995

Ring-opening polymerization (ROP) enthalpy Delta H-ROP is an important thermodynamic property controlling the polymerization of cyclic monomers. While.HROP 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.

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