Syntheses and characterization of 16‐arm star and star diblock copolymer and AB8 9‐miktoarm star copolymer via NMRP and ROP from dendritic multifunctional macroinitiators |
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| Authors: | Yozo Miura Hiroyuki Dote Hiroyuki Kubonishi Kenichi Fukuda Tomoko Saka |
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| Affiliation: | 1. Department of Applied Chemistry, Graduate School of Engineering, Osaka City University, Sumiyoshi‐ku, Osaka 558‐8585, JapanDepartment of Applied Chemistry, Graduate School of Engineering, Osaka City University, Sumiyoshi‐ku, Osaka 558‐8585, Japan;2. Department of Applied Chemistry, Graduate School of Engineering, Osaka City University, Sumiyoshi‐ku, Osaka 558‐8585, Japan |
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| Abstract: | A dendritic macroinitiator having 16 TEMPO‐based alkoxyamines, Star‐16 , was prepared by the reaction of a dendritic macroinitiator having eight TEMPO‐based alkoxyamines, [G‐3]‐OH , with 4,4′‐bis(chlorocarbonyl)biphenyl. The nitroxide‐mediated radical polymerization (NMRP) of styrene (St) from Star‐16 gave 16‐arm star polymers with PDI of 1.19–1.47, and NMPR of 4‐vinylpyridine from the 16‐arm star polymer gave 16‐arm star diblock copolymers with PDI of 1.30–1.43. The ring‐opening polymerization of ε‐caprolactone from [G‐3]‐OH and the subsequent NMRP of St gave AB8 9‐miktoarm star copolymers with PDI of 1.30–1.38. The benzyl ether linkages of the 16‐arm star polymers and the AB8 9‐miktoarm star copolymers were cleaved by treating with Me3SiI, and the resultant poly(St) arms were investigated by size exclusion chromatography (SEC). The SEC results showed PDIs of 1.23–1.28 and 1.18–1.22 for the star polymers and miktoarm stars copolymers, respectively, showing that they have well‐controlled poly(St) arms. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1159–1169, 2007. |
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| Keywords: | gel permeation chromatography living polymerization miktoarm star copolymers nitroxide polystyrene poly(4‐vinylpyridine) radical polymerization ring‐opening polymerization star polymers |
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