Molecular Simulations and Mechanistic Analysis of the Effect of CO₂ Sorption on Thermodynamics, Structure, and Local Dynamics of Molten Atactic Polystyrene

A simulation strategy encompassing different scales was applied to the systematic study of the effects of CO₂ uptake on the properties of atactic polystyrene (aPS) melts. The analysis accounted for the influence of temperature between 450 and 550 K, polymer molecular weights (M_w) between 2100 and 31000 g/mol, and CO₂ pressures up to 20 MPa on the volumetric, swelling, structural, and dynamic properties of the polymer as well as on the CO₂ solubility and diffusivity by performing molecular dynamics (MD) simulations of the system in a fully atomistic representation. A hierarchical scheme was used for the generation of the higher M_w polymer systems, which consisted of equilibration at a coarse-grained level of representation through efficient connectivity-altering Monte Carlo simulations, and reverse-mapping back to the atomistic representation, obtaining the configurations used for subsequent MD simulations. Sorption isotherms and associated swelling effects were determined by using an iterative procedure that incorporated a series of MD simulations in the NPT ensemble and the Widom test particle insertion method, while CO₂ diffusion coefficients were extracted from long MD runs in the NVE ensemble. Solubility and diffusivity compared favorably with experimental results and with predictions of the Sanchez-Lacombe equation of state, which was reparametrized to capture the M_w dependence of polymer properties with greater accuracy. Structural features of the polymer matrix were correctly reproduced by the simulations, and the effects of gas concentration and M_w on structure and local dynamics were thoroughly investigated. In the presence of CO₂, a significant acceleration of the segmental dynamics of the polymer occurred, more pronouncedly at low M_w. The speed-up effect caused by the swelling agent was not limited to the chain ends but affected the whole chain in a similar fashion.