Unexpected toroidal micelles formed from St/MMA gradient copolymers

Toroidal micelles are of great interest and rarely observed in gradient copolymer systems. Herein, we report massive toroidal micelles formed from styrene (St)/methyl methacrylate (MMA) gradient copolymers using a common solvent mixing method followed by a cooling-heating procedure. Furthermore, we demonstrate that the obtained toroidal morphology is sensitively dependent on a heat treatment procedure. Solely spherical micelles are obtained by a common solvent mixing method. These spherical micelles could be transformed into toroidal micelles via vesicles during a cooling-heating process. When a reverse heating-cooling process is adopted, no toroidal micelles formed. Thus, these results add new members to the family of toroidal micelles and reveal pathway dominating morphologies in gradient copolymer micelles.