Fundamentals of RAFT Miniemulsion Polymerization Kinetics

The polymerization rate of RAFT-mediated miniemulsion polymerization, in which the time fraction of active radical phi A is larger than a few percent, basically increases with reducing the particle size. For smaller particle sizes, however, the statistical variation of monomer concentration among particles may slow down the polymerization rate. The rate retardation by increasing the RAFT concentration occurs with or without the intermediate termination in a zero-one system. According to the present theoretical investigation, smaller particles are advantageous in implementing a faster polymerization rate, a narrower MWD, and a smaller number of dead polymer chains.