Exploiting Seeded RAFT Polymerization for the Preparation of Graft Copolymer Nanoparticles.

Although seeded reversible addition-fragmentation chain transfer (RAFT) polymerization is explored as a unique method for the preparation of block copolymer nanoparticles with diverse structures, the preparation of nonlinear polymer nanoparticles by seeded RAFT polymerization is rarely reported. Herein, linear block copolymer nanoparticles are first prepared by RAFT dispersion copolymerization of benzyl methacrylate (BzMA) and 2-(2-(n-butyltrithiocarbonate)propionate)ethyl methacrylate (BTPEMA) with different [BzMA]/[BTPEMA] ratios, and employed as seeds for seeded RAFT polymerization of isobornyl acrylate (IBOA) to prepare graft copolymer nanoparticles with different numbers of PIBOA side chains. Comparing with linear triblock copolymers with the same chemical composition, the graft copolymers can promote the formation of higher-order morphologies (e.g., vesicles) under seeded RAFT polymerization conditions. Effects of reaction parameters on the morphology of graft copolymer nanoparticles are investigated in detail, and two morphological phase diagrams are constructed. It is expected that this study will not only expand the scope of seeded RAFT polymerization but also offer new opportunities for the preparation of unique polymer nanoparticles.