Molecular Dynamics Study of the Swelling of Poly(methyl methacrylate) in Supercritical Carbon Dioxide

Materials. 2019. Vol. 12. No. 20. P. 3315.

Gurina D., Budkov Y., Kiselev M. G.

The swelling of a poly (methyl methacrylate) in supercritical carbon dioxide was studied by means of full atomistic classical molecular dynamics simulation. In order to characterize the polymer swelling, we calculated various properties related to the density, structure, and dynamics of polymer chains as a function of the simulation time, temperature, and pressure. In addition, we compared the properties of the macromolecular chains in supercritical CO2 with the properties of the corresponding bulk system at the same temperature and atmospheric pressure. It was shown that diffusion of CO2 molecules into the polymer led to a significant increase in the chain mobility and distances between them. Analysis of diffusion coefficients of CO2 molecules inside and outside the poly(methyl methacrylate) sample has shown that carbon dioxide actively interacts with the functional groups of poly (methyl methacrylate). Joint analysis of the radial distribution functions obtained from classical molecular dynamics and of the averaging interatomic distances from Car-Parrinello molecular dynamics allows us to make a conclusion about the possibility of formation of weak hydrogen bonds between the carbon dioxide oxygen atom and the hydrogen atoms of the polymer methyl groups.

Keywords: молекулярная динамика, Molecular Dynamics Simulations, сверхкритические флюиды, Supercritical fluids, Swelling, Набухание полимеров