Micellar nucleation differential microemulsion polymerization

Polymer nanoparticles within the range of 2–5 nm with a solid content of more than 13 wt.% and a narrow molecular weight polydispersity (Mw/Mn ∼ 1.1) were for the first time prepared using a micellar nucleation differential microemulsion polymerization system emulsified by sodium dodecyl sulfate (SDS), with SDS/monomer (methyl methacrylate) and SDS/H2O weight ratios of up to 1:16 and 1:100, respectively. It was found that for benzoyl peroxide (BPO), micellar nucleation is more favorable for the synthesis of smaller polymer nanoparticles than ammonium persulfate (APS) which gives rise to homogeneous nucleation and 2,2′-azobisisobutyronitrile (AIBN) which involves partially heterogeneous nucleation. In the polymerization process, there exists a critical stability concentration (CSC) of SDS, above which the size of the nanoparticles is to be minimized and stabilized. With an increase in the monomer addition rate, the polymerization system changes from a microemulsion system to an emulsion system. A mechanism was proposed to describe the micellar nucleation process of differential microemulsion polymerization. This study may contribute to the development of fine polymer nanoparticles for drug delivery systems.