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Synthesis of AB2 3‐ and AB4 5‐Miktoarm Star Copolymers Initiated from Dendritic Tri‐ and Penta‐Functional Initiators by Combination of Ring‐Opening Polymerization of ε‐Caprolactone and Nitroxide‐Mediated Radical Polymerization of Styrene
Authors:Yozo Miura  Yumi Sakai  Keisuke Yamaoka
Abstract:Summary: Well‐defined AB2 3‐ and AB4 5‐miktoarm star copolymers were prepared by combination of ring‐opening polymerization (ROP) and nitroxide‐mediated radical polymerization (NMRP) using dendritic tri‐ and penta‐functional initiators. Initially, two kinds of dendritic initiators having one benzylic OH and two or four TEMPO‐based alkoxyamine moieties were prepared. Using them, ROP of ε‐caprolactone was carried out at room temperature to give poly(ε‐caprolactone)s carrying two or four alkoxyamine moieties. NMRP of styrene from the poly(ε‐caprolactone)s was carried out at 120 °C to give AB2 3‐ and AB4 5‐miktoarm star copolymers, which were analyzed by 1H NMR and SEC. The equation image increased linearly with conversion and the equation image were in the range 1.10–1.37, showing that well‐defined AB2 3‐ and AB4 5‐miktoarm star copolymers were formed.
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Well‐defined AB2 3‐ and AB4 5‐miktoarm star copolymers were prepared by combination of ring‐opening polymerization (ROP) and nitroxide‐mediated radical polymerization (NMRP) using dendritic tri‐ and penta‐functional initiators.

Keywords:living polymerization  molecular weight distribution/molar mass distribution  radical polymerization  ring‐opening polymerization  star polymers
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