Combining Crystallization-Driven Self-Assembly with Reverse Sequence Polymerization-Induced Self-Assembly Enables the Efficient Synthesis of Hydrolytically Degradable Anisotropic Block Copolymer Nano-objects Directly in Concentrated Aqueous Media

Herein we combine the well-known processing advantages conferred by polymerization-induced self-assembly (PISA) with crystallization-driven self-assembly (CDSA) to achieve the efficient synthesis of hydrolytically degradable, highly anisotropic block copolymer nano-objects directly in aqueous solution at 30% w/w solids. This new strategy involves a so-called reverse sequence PISA protocol that employs poly­(l-lactide) (PLLA) as the crystallizable core-forming block and poly­(N,N′-dimethylacrylamide) (PDMAC) as the water-soluble non-ionic coronal block. Such syntheses result in PDMAC-rich anisotropic nanoparticles. Depending on the target diblock copolymer composition, either rod-like nanoparticles or diamond-like platelets can be obtained. Furthermore, N-Acryloylmorpholine is briefly evaluated as an alternative hydrophilic vinyl monomer to DMAC. Given that the PLLA block can undergo either hydrolytic or enzymatic degradation, such nanoparticles are expected to offer potential applications in various fields, including next-generation sustainable Pickering emulsifiers.