Arm-first method as a simple and general method for synthesis of miktoarm star copolymers

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Gao, Haifeng [1 ]
Matyjaszewski, Krzysztof [1 ]
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[1] Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213, United States
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Miktoarm star copolymers containing two or more arm species were synthesized by atom transfer radical polymerization using a simple and general arm-first method; that is; one-pot cross-linking a mixture of different linear macroinitiator (MI) species by a divinyl cross-linker; such as divinylbenzene. Using linear MIs with a high degree of bromine chain-end functionality; including polyacrylate; polystyrene; polymethacrylate and poly(ethylene oxide); resulted in high-yield star polymers (>90%); Characterized by liquid adsorption chromatography techniques; which separated star polymers on the basis of the chemical composition of arms; the obtained star product was proved to be miktoarm star copolymers containing two or more arm species in one molecule; instead of mixture of different homoarm star polymers. Within our investigation; the molar ratios of the arms in the miktoarm star copolymers were always in agreement with the composition of the initial MI mixture; indicating the powerful capacity of this arm-first method for synthesis of miktoarm star copolymers with potentially any molar ratios and species of the arms. By using a mixture containing five types of linear MIs with different chemical compositions; miktoarm star copolymers containing five kinds of arms were synthesized for the first time; which significantly expanded the methodologies for synthesis of miktoarm star copolymers by living polymerization techniques. © 2007 American Chemical Society;
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页码:11828 / 11834
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