Synthesis of Poly(δ-valerolactone)-poly( <i>N,N</i> -dimethylacrylamide) Supermicelles in Concentrated Aqueous Media via Reverse Sequence Polymerization-Induced Self-Assembly

≤ 1.29) being achieved for this RAFT polymerization. The initial copolymer morphology is ill-defined; however, depending on the target PVL-PDMAC composition, either anisotropic semiflexible rod-like particles or so-called supermicelles can be formed on aging such PVL-PDMAC diblock copolymer dispersions for up to 19 weeks at 20 °C. This is attributed to slow crystallization of the PVL block, which is initially amorphous immediately after synthesis, as judged by X-ray diffraction studies, but gradually becomes more semicrystalline on aging. Thus, the evolution in copolymer morphology is driven by crystallization-driven self-assembly (CDSA). The aged nanoparticles were characterized by transmission electron microscopy and small-angle X-ray scattering. The semiflexible rods were also subjected to shear-induced polarized light imaging analysis, with shear-induced alignment remaining for up to 1 h after cessation of shear.