Abstract
Compartmentalization of a nitroxide-mediated radical polymerization system can lead to improved levels of both control and livingness, but at the cost of a reduced polymerization rate. Improved control is a result of the confined space effect on deactivation, whereas improved livingness stems from the segregation effect on bimolecular termination. Modelling and simulations have been carried out for the systems styrene/2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and styrene/2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxy (TIPNO) using the respective nitroxide-based polystyrene macroinitaitors (alkoxyamines) at 125°C to elucidate whether similar benefits can be obtained in the corresponding bulk polymerizations by merely diluting the systems or by addition of extra free nitroxide. The results have shown that neither approach leads to simultaneous improvement in control and livingness relative to the corresponding bulk systems, thus accentuating the merits of compartmentalization in nanoreactors.
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