Controlled/living radical polymerization in nanoreactors: compartmentalization effects

Compartmentalization in nanoreactors, i.e. the confinement of reactants to monomer droplets or polymer particles with diameters in the approximate range 20-200 nm, may have a marked beneficial effect on the progression of a controlled/living radical polymerization based on the persistent radical effect such as nitroxide-mediated radical polymerization and atom transfer radical polymerization. Compartmentalization effects comprise the confined space effect, which acts to improve the control over the molecular weight distribution (narrower) and the segregation effect which results in increased livingness (end-functionality). Exploitation of nanoreactors thus offers novel means of improving the performance of controlled/living radical polymerizations.