Structure and dynamics of stereo-regular poly(methyl-methacrylate) melts through atomistic molecular dynamics simulations.

Poly(methyl-methacrylate), PMMA, is a disubstituted vinyl polymer whose properties depend significantly on its tacticity. Here we present a detailed study of the structure, conformation, and dynamics of syndiotactic, atactic, and isotactic PMMA melts at various temperatures (580, 550, 520, and 490 K) via all-atom molecular dynamics simulations. The calculated volumetric properties are close to experimental data. The T and chain dimensions of PMMA model systems are found to depend strongly on tacticity in agreement with experimental findings. The backbone bonds in trans (t), diads in tt, and inter-diads in t|t torsional states are the most populated for all PMMA stereo-chemistries and their fractions increase with the number of syndiotactic sequences. Also, the effective torsional barrier heights for the backbone, ester side group, and α-methyl group are larger for syndiotactic PMMA compared to the isotactic one. The structure of the PMMA chains is studied by computing the intra- and inter-chain static structure factors, S(q), and the radial pair distribution functions. In the first peak of S(q), both intra- and inter-chain components contribute, whereas the second and third peaks mainly come from inter- and intra-chain parts, respectively. For all PMMA stereo-isomers a clear tendency of ester-methyl groups to aggregate is observed. The local dynamics are studied by analyzing torsional autocorrelation functions for various dihedral angles. A wide spectrum of correlation times and different activation energies are observed for the motions of different parts of PMMA chains. The stereo-chemistry affects the backbone, ester side group, and α-methyl motions, whereas the ester-methyl rotation remains unaffected. The dynamic heterogeneity of the PMMA chains is also studied in detail for the different stereo-chemistries via the temperature dependence of the stretching exponent. Furthermore, the reorientational dynamics at the chain level and translational dynamics for monomer and chain centers-of-mass are analyzed.