Ionic and Nonspherical Polymer Nanoparticles in Nonpolar Solvents

A series of ionic diblock copolymer nanoparticles was prepared in a typical nonpolar solvent (n-dodecane) via polymerization-induced self-assembly (PISA). A single cationic repeat unit was incorporated into the poly(stearyl methacrylate) (PSMA) stabilizer of otherwise uncharged poly(stearyl methacrylate)–poly(benzyl methacrylate) (PSMA–PBzMA) diblock copolymer nanoparticles. By using short PSMA stabilizer blocks, it was possible to obtain nanoparticles with the range of morphologies expected (spheres, worms, and vesicles). For nanoparticles where all stabilizer chains possessed an ionic group, higher-order morphologies were obtained at lower PBzMA degrees of polymerization than corresponding uncharged particles, and the particles were electrophoretic. For nanoparticles where only a fraction of the stabilizer chains contained an ionic group, higher-order morphologies were obtained at precisely the same PBzMA degrees of polymerization, and the electrophoretic response was greater than when the shell was fully ionic. These particles with a partially ionic shell are a fascinating system, providing morphologies that can be predicted from the existing knowledge of the diblock copolymer morphology yet with the highest possible electrophoretic mobility.