Mimicking Block Copolymer Self‐Assembly with One‐Pot Synthesized Polyphosphoester Gradient Copolymers

Abstract The development of sustainable and especially (bio)degradable nanomaterials is an important aspect of addressing environmental concerns of persistent commodity polymers. This study explores the synthesis of degradable amphiphilic polyphosphoester (PPE) gradient copolymers (GCPs) and block copolymers (BCPs) and their self‐assembly in aqueous solution. The polymers are synthesized via ring‐opening polymerization (one‐pot or sequential), enabling precise control over their chemical composition and molar mass. Self‐assembly in aqueous solution resulted in the formation of diverse nanostructures, including cylindrical micelles and polymersomes. The influence of gradient strength on self‐assembly is examined and demonstrates that subtle variations in copolymer composition impact the resulting morphologies. Furthermore, the controlled hydrolysis of polymersomes are demonstrated, leading to the release of encapsulated cargo depending on the pH of the solution. The successful synthesis and characterization of these degradable PPE‐based nanomaterials provide a promising platform for the development of sustainable nanocarriers with applications in various fields, including drug or agrochemical delivery.