Scalable and uniform 1D nanoparticles by synchronous polymerization, crystallization and self-assembly

The preparation of well-defined nanoparticles based on soft matter, using solution-processing techniques on a commercially viable scale, is a major challenge of widespread importance. Self-assembly of block copolymers in solvents that selectively solvate one of the segments provides a promising route to core-corona nanoparticles (micelles) with a wide range of potential uses. Nevertheless, significant limitations to this approach also exist. For example, the solution processing of block copolymers generally follows a separate synthesis step and is normally performed at high dilution. Moreover, non-spherical micelles—which are promising for many applications—are generally difficult to access, samples are polydisperse and precise dimensional control is not possible. Here we demonstrate the formation of platelet and cylindrical micelles at concentrations up to 25% solids via a one-pot approach—starting from monomers—that combines polymerization-induced and crystallization-driven self-assembly. We also show that performing the procedure in the presence of small seed micelles allows the scalable formation of low dispersity samples of cylindrical micelles of controlled length up to three micrometres. A scalable, one-pot, solution-based protocol for the controlled synthesis of uniform non-spherical block copolymer micelles is a desirable but challenging target. Now, a polymerization-induced crystallization-driven self-assembly process has been developed that offers facile access to 1D and platelet micelle morphologies and to near monodisperse cylinders of controlled length.