Synthesis of polystyrene-poly(tert-butyl methacrylate)-poly(ethylene oxide) triarm star block copolymers

• Published in: Journal of polymer science. Part A, Polymer chemistry Polymer chemistry, 2004-04, Vol.42 (7), p.1745-1751
• Main Authors: Nasser-Eddine, Mohamad, Reutenauer, Simone, Delaite, Christelle, Hurtrez, Guy, Dumas, Philippe
• Format: Article
• Language: English
• Subjects: anionic polymerization; Applied sciences; atom transfer radical polymerizaiton; block copolymers; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; star polymers
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.20019

Three alternative routes, using the heterobifunctional macroinitiator technique, have been developed to obtain polystyrene–poly(tert‐butyl methacrylate)–poly(ethylene oxide) triarm star block copolymers. Only the route showing the reverse initiation of tert‐butyl methacrylate on potassium alkoxide leads to the pure star, whereas the other strategies lead to incomplete initiation because of either an increase in the side reactions, such as transesterification, or a decrease in the accessibility toward bulky catalysts. These limits are linked to the particular location of the initiating group at the junction of the two blocks of the copolymer precursor. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1745–1751, 2004 Polystyrene–poly(tert‐butyl methacrylate)–poly(ethylene oxide) triarm star block copolymers have been synthesized with a heterobifunctional macroinitiator (1). Three alternative strategies, using living anionic and/or controlled radical polymerization techniques, have been developed. Only the reverse initiation of tert‐butyl methacrylate on potassium alkoxide leads to a pure star. This shows the possibilities and limits of such an approach.