Synthesis of ABCD 4‐Miktoarm star‐shaped quarterpolymers by combination of the “click” chemistry with multiple polymerization mechanism |
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Authors: | Guowei Wang Xiaolan Luo Chao Liu Junlian Huang |
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Institution: | The Key Laboratory of Molecular Engineering of Polymers, State Education Ministry of China, Department of Macromolecular Science, Fudan University, Shanghai 200433, China |
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Abstract: | Well‐defined ABCD 4‐Miktoarm star‐shaped quarterpolymers of poly(styrene)‐poly(tert‐butyl acrylate)‐poly(ethylene oxide)‐poly(isoprene)] star(PS‐PtBA‐PEO‐PI)] were successfully synthesized by the combination of the “click” chemistry and multiple polymerization mechanism. First, the poly(styryl)lithium (PS?Li+) and the poly(isoprene)lithium (PI?Li+) were capped by ethoxyethyl glycidyl ether (EEGE) to form the PS and PI with both an active ω‐hydroxyl group and an ω′‐ethoxyethyl‐protected hydroxyl group, respectively. After these two hydroxyl groups were selectively modified to propargyl and 2‐bromoisobutyryl group for PS, the resulted PS was used as macroinitiator for ATRP of tBA monomer and the diblock copolymer PS‐b‐PtBA with a propargyl group at the junction point was achieved. Then, using the functionalized PI as macroinitiator for ROP of EO monomer and bromoethane as blocking agent, the diblock copolymer PI‐b‐PEO with a protected hydroxyl group at the conjunction point was synthesized. After the hydrolysis, the recovered hydroxyl group of PI‐b‐PEO was modified to bromoacetyl and then azide group successively. Finally, the “click” chemistry between them was proceeded smoothly. The obtained star‐shaped quarterpolymers and intermediates were characterized by 1H NMR, FT‐IR, and SEC in detail. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2154–2166, 2008 |
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Keywords: | anionic polymerization atom transfer radical polymerization click chemistry quarterpolymers ring‐opening polymerization |
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