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 (M̄n = 3800 g mol -1; D = 1.17). RAFT polymerization with DEA affords block copolymers as evidenced by 1H NMR spectroscopy as well as size exclusion chromatography (6400 ≤ M̄n≤ 33700 g mol-1; 1.31 ≤D 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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.