Tertiary Amine Methacrylate-Based ABC Triblock Copolymers: Synthesis, Characterization, and Self-Assembly in both Aqueous and Nonaqueous Media

• Published in: Macromolecular chemistry and physics 2011-06, Vol.212 (11), p.1115-1128
• Main Authors: Bütün, Vural, Taktak, Fadime Fulya, Tuncer, Cansel
• Format: Article
• Language: English
• Subjects: Applied sciences; Copolymerization; core-shell polymers; cross-linking; Exact sciences and technology; micelles; Organic polymers; Physicochemistry of polymers; Preparation, kinetics, thermodynamics, mechanism and catalysts; self-assembly; triblock copolymer
• ISSN: 1022-1352; 1521-3935
• DOI: 10.1002/macp.201100057

Water soluble poly[2‐(diisopropylamino)ethyl methacrylate]‐block‐poly[2‐(dimethylamino) ethyl methacrylate]‐block‐poly[2‐(N‐morpholino)ethyl methacrylate] triblock copolymers are synthesized via group transfer polymerization. They are molecularly soluble in acidic solution but give PDPA‐core three‐layer “onion‐like” micelles in alkaline solution. They also give two types of micelles in hexane depending on whether a cosolvent is used: i) PMEMA‐core “onion‐like” reverse micelles are formed with a cosolvent, or, ii) [PDMA‐b‐PMEMA]‐core core–shell micelles without. In addition, novel shell cross‐linked micelles and reverse SCL micelles are also synthesized by cross‐linking the inner PDMA shell of both PDPA‐core micelles in water and PMEMA‐core reverse micelles in hexane. Well‐defined ABC triblock copolymers are synthesized via GTP. They dissolve molecularly in acidic solution and form A‐core three‐layer “onion‐like” micelles at pH 8.0. They also form both C‐core reverse micelles and BC‐core core–shell micelles in hexane depending on whether cosolvent is used. Finally, two types of novel shell cross‐linked micelles (A‐core in water and C‐core in hexane) are prepared from these remarkable ABC triblock copolymers.