Molecular dynamics simulation of mechanical relaxation of poly(propyleneimine) dendrimers

Abstract

We report on shear-stress relaxation of melts of poly(propyleneimine) (PPI) dendrimers of different generations (G2–G5). The aim of this study was to confirm our previous conclusion in Sheveleva et al. [Phys. Chem. Chem. Phys. 24, 13049–13056 (2022)] for carbosilane dendrimers that an impenetrable inner region leads to the manifestation of the crowded environment effect. The systems of PPI dendrimer melts are studied using atomistic molecular dynamics simulations. The time and frequency dependencies of the dynamic shear-stress modulus are investigated. The results are in good agreement with the available rheological experimental data for G2–G4 PPI. We have found that the crowded environment effect does not manifest itself in the mechanical relaxation of G4 PPI dendrimers in contrast to G4 carbosilane dendrimers. Despite their similar topology and close sizes, G4 PPI does not form an impenetrable core. The G5 PPI dendrimer has an impenetrable inner region, and the crowded environment effect is observed. As in carbosilane dendrimers, the maximal time of mechanical relaxation is increased due to the crowded environment effect. However, the opposite situation is for the rotational diffusion of the G5 PPI dendrimers. In contrast to carbosilane dendrimers, the rotational mobility of G5 PPI significantly slows down even taking into account the increase in the dendrimer size. The hydrogen bonding between PPI dendrimers affects the mechanical relaxation at high frequencies (short times) and enhances with growing G.