e present work, theoretical investigations have been carried out based on simulations using the previously developed modified Smith–Ewart equations for NMP [13] and [16] in order to elucidate what factors govern the extent of the segregation effect in NMP in dispersed systems. Ultimately it is hoped that the findings reported herein will aid in future endeavours to exploit particle size and compartmentalization to improve the performance of NMP (as well as other CLRP systems based on the persistent radical effect, e.g. ATRP) in dispersed systems mainly with regards to livingness and thus also the maximum attainable molecular weight.