Simultaneous Bulk- and Surface-initiated Living Polymerization Studied with a Heterogeneous Stochastic Reaction Model

To better characterize the properties of surface-initiated polymers, simultaneous bulk- and surface-initiated polymerizations are usually carried out by assuming that the properties of the surface-initiated polymers resemble those of the bulk-initiated polymers. Through a Monte Carlo simulation using a heterogeneous stochastic reaction model, it was discovered that the bulk-initiated polymers exhibit a higher molecular weight and a lower dispersity than the corresponding surface-initiated polymers, which indicates that the equivalent assumption is invalid. Furthermore, the molecular weight distributions of the two types of polymers are also different, suggesting different polymerization mechanisms. The results can be simply explained by the heterogeneous distributions of reactants in the system. This study is helpful to better understand surface-initiated polymerization.

Automated summary

Through Monte Carlo simulation, this study revealed that there are differences in molecular weight, dispersity, and molecular weight distribution between bulk-initiated polymers and surface-initiated polymers, indicating the invalidity of the equivalent assumption. The heterogeneous distribution of reactants in the system was identified as the main factor contributing to these differences.