Can We Push Rapid Reversible Deactivation Radical Polymerizations toward Immortality?

All reversible deactivation radical polymerization (RDRP) processes require a compromise between the rate of polymerization, which requires a high radical concentration, and retention of chain end functionality, which requires a low radical concentration. Here, we demonstrate that this compromise may be partially averted where fast deactivation of the propagating radical occurs. It is shown that, contrary to the predictions of classical reaction kinetics, when the probability density functions of the termination reactions are adjusted to take into account the time needed for radical diffusion, a reduction in the extent of termination can be expected if chain deactivation is rapid. We subsequently use this framework to explain experimental results in the copper(0)-mediated polymerization of acrylamide. The main concept put forward in the paper questions the commonly held assumptions of the limitations of RDRP processes and suggests the ability for a seemingly impossible level of control of radical reactions.