Daria Lazarenko, Graham P. Schmidt, Michael F. Crowley, Gregg T. Beckham and Brandon C. Knott*,
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Molecular Details of Polyester Decrystallization via Molecular Simulation
Waste polyesters are a potential feedstock for recycled and upcycled products. These polymers are generally semicrystalline, which presents a challenge for chemical and biological recycling to monomers, and thus the thermodynamic work associated with polyester decrystallization is an important consideration in some depolymerization strategies. Here, we use molecular dynamics simulations to calculate the free energy required to decrystallize a single chain from the crystal surface of five commercially and scientifically important, semiaromatic polyesters (PET, PTT, PBT, PEN, and PEF) in water. Our results indicate the decrystallization work ranges from approximately 15 kcal/mol (PEN) to 8 kcal/mol (PEF) per repeat unit for chains in the middle of a crystal surface. The insight gained into the molecular interactions that form the structural basis of semicrystalline synthetic polyesters can guide the pursuit of more efficient plastic processing, which could include catalyst development, optimizing recycling conditions including pretreatment, enzyme and solvent selections, and design of new materials.
期刊介绍:
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.