Simultaneous polymer chain growth with the coexistence of bulk and surface initiators: insight from computer simulations.

By Brownian dynamics simulations we study the simultaneous polymer chain growth process with the coexistence of bulk and surface initiators. We find that when the surface initiator density is low enough, the practical experimental way to estimate the dispersity (D) of surface-initiated chains on the basis of the dispersity of bulk-initiated chains remains valid as long as the conformations of grafted chains remain within the mushroom regime (i.e., the grafted chains are sparsely distributed). On the other hand, although the average chain lengths of surface and bulk polymers could be equivalent when certain conditions are met, their mass distributions are still different. We also find that increasing the fraction of surface initiators leads to an enlarged disparity in D and average length between surface and bulk chains, which is inconsistent with previous studies. This study helps in better understanding the cooperative competition and suppressing effect of bulk chains on surface grown chains, as well as the cause of the dispersity of the surface grown chains as compared to their bulk counterparts with the coexistence of bulk and surface initiators.