Efficient Synthesis of Sterically-Stabilized Nano-Objects via RAFT Dispersion Polymerization of Benzyl Methacrylate in Alcoholic Media

Synthesis of diblock copolymer nano‐objects: alcohol is a good idea! RAFT dispersion polymerization of benzyl methacrylate in alcohol using weak polyelectrolyte‐based chain transfer agents allows the facile synthesis of sterically stabilized diblock copolymer nano‐objects with very high monomer conversions. Such syntheses are usually problematic when conducted in water due to electrostatic repulsion between highly charged stabilizer chains, which impedes in situ self‐assembly. Construction of a detailed phase diagram facilitates reproducible syntheses of well‐defined diblock copolymer spheres, worms or vesicles, since it allows mixed phase regions to be avoided. Aqueous electrophoresis studies confirm that these nano‐objects can acquire substantial surface charge when transferred to aqueous solution due to ionization (or protonation) of the polyacid (or polybase) stabilizer chains.