Grand canonical molecular dynamics simulation of surface-initiated polymerization

The post-characterization of polymer brushes prepared from surface-initiated polymerization (SIP) is challenging because of their unique morphology and limitations in experimental techniques. However, in simulation counterparts, it is much easier to gain control over SIP processes. In this work, we used grand canonical molecular dynamics simulations to investigate the growth kinetics and characterization of polymer brushes. The SIP was studied by varying the grafting density. At low grafting densities, nearly monodisperse brushes were obtained. The dispersity was found to be increased with increasing grafting density; as a result, brushes with broad molecular weight distribution were obtained. We also showed that parameters such as thickness, molecular weight, and dispersity can be precisely controlled during SIP. The results suggests that the method presented here provides strategies to synthesize polymer brushes and tailor their properties more efficiently.