Individually Addressable Thermo‐ and Redox‐Responsive Block Copolymers by Combining Anionic Polymerization and RAFT Protocols

A novel diblock copolymer consisting of poly(vinylferrocene) (PVFc) and poly(N,N-diethylacrylamide) (PDEA) is synthesized via a combination of anionic and RAFT polymerization. The use of a novel route to hydroxyl-end-functionalized metallopolymers in anionic polymerization and subsequent esterification with a RAFT agent leads to a PVFc macro-CTA (M¯n = 3800 g mol(-1) ; Đ = 1.17). RAFT polymerization with DEA affords block copolymers as evidenced by (1) H NMR spectroscopy as well as size exclusion chromatography (6400 ≤ M¯n≤ 33700 g mol(-1) ; 1.31 ≤ Đ 1.28). Self-assembly of the amphiphilic block copolymers in aqueous solution leads to micelles as shown via TEM. Importantly, the distinct thermo-responsive and redox-responsive character of the blocks is probed via dynamic light scattering and found to be individually and repeatedly addressable.