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Polypropylene (PP) is widely used and currently very little recycled. A promising method for recycling the PP present in plastic waste involves its selective dissolution and subsequent separation from undissolved compounds. We address here the fundamentals of PP dissolution. Specifically, we present a model that describes the different phenomena involved in the dissolution of semicrystalline PP and validate the model with the experimental results on the decrystallization and dissolution kinetics of PP pellets. The model provides detailed time-resolved and position-resolved information on composition (i.e., crystalline PP, amorphous PP, and solvent) and solvent diffusivity (which depends on composition) across the dissolving polymer particle, in different solvents and temperatures. Such information is unavailable experimentally or difficult to obtain. The key fitted parameters that capture decrystallization and polymer chain disentanglement decrease with increasing temperature following an Arrhenius relationship, with activation energies higher than that for crystallization and comparable to that for melt viscosity. Both decrystallization and dissolution times increase with particle size. For smaller particles, decrystallization and dissolution occur nearly simultaneously, while for larger particles, their interior remains solvent-poor and crystalline for longer times. This work offers insights into the interplay of decrystallization and polymer chain disentanglement during the time-course of PP dissolution. Further, this work facilitates the design and optimization of a dissolution–precipitation recycling process that can unlock value from the million tons of PP annually that is currently being landfilled or incinerated following its use. 

ABSTRACT Elucidating the crystalline‐amorphous interface during decrystallization processes in semi‐crystalline polyethylene (PE) is crucial for the advancement of polymer theory and plastic‐to‐plastic recycling technologies. In this study, we carried out an in‐depth investigation of PE thin films undergoing melting or dissolution using a temperature‐controlled liquid flow‐cell experimental setup which provided in situ mid‐infrared (MIR, 4000–700 cm⁻¹) and near‐infrared (NIR, 6000–4000 cm⁻¹) spectra in real time. The spectroscopic results yielded molecular‐level information regarding PE decrystallization and chain disentanglement via fundamental vibrations, combination bands, and overtones which were correlated using hetero‐spectral two‐dimensional correlation spectroscopy (2D‐COS). A quantitative procedure for the calculation of PE degree of crystallinity was developed to track transformations of crystalline domains during melting and dissolution. This semi‐empirical model achieved a strong linear correlation of at least +0.93 in four spectral regions: 750–700 cm⁻¹, 1500–1400 cm⁻¹, 3000–2800 cm⁻¹, and 4400–4200 cm⁻¹. This analysis revealed important spectral trends about the interfacial solvation environment during these processes. Lastly, the time evolution of the unraveling, terminal methyl (CH₃) groups of PE cilia was examined in relation to the decrystallization mechanism of PE. The insights obtained from this study advance the fundamental understanding necessary for developing new depolymerization and dissolution‐precipitation recycling strategies.