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

Area of Science:

• Polymer Chemistry
• Computational Chemistry
• Materials Science

Background:

• Ring-opening polymerization (ROP) enthalpy (ΔHROP) is crucial for controlling cyclic monomer polymerization.
• Accurate computation of ΔHROP (within 5-10 kJ/mol) is vital for designing depolymerizable polymers.
• Existing computational methods face challenges in accuracy for realistic polymer systems.

Purpose of the Study:

• To develop a first-principles computational scheme for precise ΔHROP calculation.
• To overcome challenges in conformational exploration and finite size effects in ROP enthalpy computations.
• To validate the new scheme against experimental data for a diverse set of ROP polymers.

Main Methods:

• Developed a first-principles computational scheme to address challenges in ΔHROP calculation.
• Incorporated extensive conformational state exploration.
• Accounted for finite size effects in the computational model.
• Validated the scheme using a benchmark set of 42 ROP polymers with experimental ΔHROP values.

Main Results:

• Achieved a root-mean-square error of approximately 7 kJ/mol for ΔHROP predictions on the benchmark set.
• Demonstrated a 3-fold improvement in accuracy compared to conventional computational approaches.
• Successfully validated the computational scheme against reliable experimental data.

Conclusions:

• The developed computational scheme significantly enhances the accuracy of ROP enthalpy predictions.
• This breakthrough enables the creation of high-quality ΔHROP databases for machine learning models.
• Accelerates the design and discovery of new depolymerizable polymers with tailored properties.