The Competition of Termination and Shielding to Evaluate the Success of Surface-Initiated Reversible Deactivation Radical Polymerization.

One of the challenges for brush synthesis for advanced bioinspired applications using surface-initiated reversible deactivation radical polymerization (SI-RDRP) is the understanding of the relevance of confinement on the reaction probabilities and specifically the role of termination reactions. The present work puts forward a new matrix-based kinetic Monte Carlo platform with an implicit reaction scheme capable of evaluating the growth pattern of individual free and tethered chains in three-dimensional format during SI-RDRP. For illustration purposes, emphasis is on normal SI-atom transfer radical polymerization, introducing concepts such as the apparent livingness and the molecular height distribution (MHD). The former is determined based on the combination of the disturbing impact of termination (related to conventional livingness) and shielding of deactivated species (additional correction due to hindrance), and the latter allows structure-property relationships to be identified, starting at the molecular level in view of future brush characterization. It is shown that under well-defined SI-RDRP conditions the contribution of (shorter) hindered dormant chains is relevant and more pronounced for higher average initiator coverages, despite the fraction of dead chains being less. A dominance of surface-solution termination is also put forward, considering two extreme diffusion modes, i.e., translational and segmental. With the translational mode termination is largely suppressed and the living limit is mimicked, whereas with the segmental mode termination occurs more and the termination front moves upward alongside the polymer layer growth. In any case, bimodalities are established for the tethered chains both on the level of the chain length distribution and the MHD.