“Living” Polymer Dispersity Quantification for Nitroxide-Mediated Polymerization Systems by Mimicking a Monodispersed Polymer Blending Strategy

The quantification of dispersity is an indispensable part of characterizing polymers. In this work, general dispersity equations for “living” polymers obtained by nitroxide-mediated polymerization (NMP), reflecting the contribution of dead polymeric chains to the overall dispersity, are presented. Derivation of new dispersity equations is inspired by the monodispersed polymer blending strategy, which is confirmed by experimental data in accordance with a Gaussian distribution. The accuracy and applicability of the newly derived equations are validated by comparative studies with those by the conventional equations through an in silico simulation benchmark and experimental data gathered from literature studies. Moreover, the dissociation and combination reaction rate coefficients are also successfully estimated by the combination of kinetic and as-developed dispersity equations under actual polymerization conditions. The new dispersity equations can be used as dispersity modulation tools in combination with the Gaussian distribution function and can also be effective tools beyond the experimentation to predict accurate dispersity for living polymers and to estimate rate coefficients.