Atomistic Insights into Structure and Properties of ε-Caprolactone Oligomers.

The design of functional and sustainable materials requires a detailed understanding of the material properties and degradation mechanisms. In particular, the design of fully biodegradable polymers could allow a quick and controlled decomposition of materials before they accumulate in the environment and break down to micro- and nanoplastics. An important degradation pathway proceeds via the hydrolysis of polyesters. To obtain the best performing material candidates, a multiscale-level understanding that takes into account electronic structure combined with multiple configurations at the macroscopic scale is necessary. In this contribution, we present the extension of the multiscale Quantum Cluster Equilibrium method to oligomer materials. We showcase the first application of this methodology to oligomer systems, in particular oligo(ε-Caprolactone). The ε-Caprolactone oligomers were synthesized and characterized comprehensively by means of NMR, SEC, DSC, and TGA. Experimentally, two melting temperatures were observed, which were predicted by theoretical calculations and are in convincing agreement.