Effect of Solvent Polarity on the Photo-Induced Polymerization-Induced Self-Assembly of Poly(tert-butyl acrylate)-block-Polystyrene near Room Temperature

Reversible addition-fragmentation chain transfer mediated polymerization-induced self-assembly (RAFT-PISA) offers an efficient approach for the preparation of polymeric nanomaterials, giving access not only to common structures such as spheres, worm-like micelles and vesicles, but also to much more complex meso-objects. However, when the core forming block polymer possesses a high glass transition temperature (Tg), like poly(methyl methacrylate) or polystyrene (PS), high-order morphologies are particularly difficult to achieve since the glassy core can prevent polymer chain reorganization during PISA. To overcome this issue, we chose to perform visible light-initiated RAFT-PISA of poly(<i>tert</i>-butyl acrylate)-<i>block</i>-polystyrene (P<i>t</i>BA-<i>b</i>-PS) in solvent systems with varying degrees of polarity. More specifically, we prepared different mixtures of diisopropyl ether and ethanol and chose P<i>t</i>BA as macro-CTA due to its broad range of solubility. By varying the ratio between ethanol and diisopropyl ether, we could observe a transition from spherical micelles to vesicles via intermediate structures (e.g., necklace-like micelles, network-like micellar aggregates and wedding rings). This result was particularly remarkable since the experiments were performed near room temperature. We believe that these multiple morphologies were induced by the interactions between the solvent and the corona and the change in swelling of the polystyrene core with styrene monomer that facilitated its rearrangement. We anticipate that this approach could be applied to other polymeric systems with high Tgs.