Experimental Evidence and Beneficial Use of Confined Space Effect in Nitroxide-Mediated Radical Microemulsion Polymerization (Microemulsion NMP) of n‑Butyl Acrylate

The confined space effect, which was found by the authors, in nitroxide-mediated radical polymerization (NMP) in a microemulsion system (microemulsion NMP) of n-butyl acrylate (BA) was investigated, where the diameter of micelles (monomer droplets) was 5–10 nm and that of poly­(BA) (PBA) particles at the completion of the polymerization was ∼60 nm. To clarify the importance of diameter of monomer droplets (d m) in the initial stage of the microemulsion NMP, NMP in a miniemulsion system (miniemulsion NMP) (d m: ∼60 nm) was carried out as a comparative experiment. The miniemulsion NMP proceeded without molecular weight distribution (MWD) control; on the other hand, in the microemulsion NMP the MWD shifted to higher molecular weight with increasing conversion. The livingnesses of PBAs obtained in the initial stages of the miniemulsion and microemulsion NMPs, which were determined by chain extension test, were 0.01% and 64%, respectively. From these results, it is concluded that the confined space effect in the initial stage of the microemulsion NMP effectively operated and resulted in PBA with predetermined molecular weight and good control of MWD even if the diameter of polymerizing particles increased with conversion.