The ethanolic reversible addition-fragmentation chain transfer dispersion polymerization (RAFTDP), at 21 wt-%, of 2-(naphthalen-2-yloxy)ethyl methacrylate (NOEMA) and 2-phenoxyethyl methacrylate (POEMA) with a poly[2-(dimethylamino)ethyl methacrylate] macro-chain transfer agent (CTA) with an average degree of polymerization of 20 (PDMAEMA20) is described. DMAEMA20-b-NOEMAy (y = 20–125) block copolymers were readily prepared under dispersion conditions in ethanol at 70°C. However, the polymerization of NOEMA was not well controlled, with size exclusion chromatograms being distinctly bi or multimodal with measured dispersities . Though NOEMA copolymerization was not ideal, the resulting series of block copolymers did exhibit the anticipated full spectrum of nanoparticle morphologies (spheres, worms, and vesicles). Interestingly, these morphology transitions occurred over a relatively narrow range of block copolymer compositions. In the case of POEMA, copolymerization was also poorly controlled with 1.50 ≤ ĐM ≤ 1.83 for the series of DMAEMA20-b-POEMAy copolymers. In contrast to the NOEMA-based copolymers, the POEMA series only yielded nanoparticles with a spherical morphology whose size increased with increasing average degrees of polymerization of the POEMA block. Collectively, though both NOEMA and POEMA can be utilized in ethanolic RAFT dispersion polymerization formulations, these preliminary studies suggest that neither appears to be an ideal aryl methacrylate choice as comonomer, especially if the goal is to combine the synthesis of well-defined copolymers with efficient nanoparticle formation.
In situ SAXS studies of a prototypical RAFT aqueous dispersion polymerization formulation: monitoring the evolution in copolymer morphology during polymerization-induced self-assembly
