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Synthesis of ABCD‐type miktoarm star copolymers and transformation into zwitterionic star copolymers
Authors:Xiaojun Wang  Junpo He  Yuliang Yang
Institution:1. Department of Macromolecular Science, Fudan University, Shanghai 200433, China;2. The Key Laboratory of Molecular Engineering of Polymers, Ministry of Education, Fudan University, Shanghai 200433, China;3. The Key Laboratory of Molecular Engineering of Polymers, Ministry of Education, Fudan University, Shanghai 200433, ChinaDepartment of Macromolecular Science, Fudan University, Shanghai 200433, China
Abstract:ABCD‐type 4‐miktoarm star copolymers of styrene (St), α‐methylstyrene (αMSt), tert‐butyl methacrylate (tBuMA), and 4‐vinylpyridine (4VP) were synthesized via anionic polymerization using 1,3‐bis(1‐phenylvinyl)benzene (m‐DDPE) as the linking molecule. The synthetic route was rationally designed with respect to the reactivity of individual propagating anion towards the double bond of m‐DDPE. Thus the synthesis includes several consecutive key reactions, for example, the monoaddition of polystyryllithium towards m‐DDPE, the polymerization of tBuMA initiated by the resulting monoadduct to produce a diblock macromonomer, the coupling of the macromonomer with poly(α‐methylstyryl)lithium to form a 3‐arm star anion, and the polymerization of 4‐vinylpyridine initiated by the star anion. These reactions were conducted either in a one‐pot process, in which the diblock macromonomer was in situ coupled with poly(α‐methylstyryl)lithium, or in a batch polymerization process, in which the same diblock macromonomer was separated. The final product was hydrolyzed to produce a zwitterionic miktoarm star copolymer, which was soluble at lower pH but insoluble in neutral and basic solution. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4818–4828, 2007
Keywords:anionic polymerization  hydrolysis  living polymerization  star copolymers  star polymer  zwitterionic polymers
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