Synthesis of well-defined AB20-type star polymers with cyclodextrin-core by combination of NMP and ATRP

• Published in: Journal of polymer science. Part A, Polymer chemistry Polymer chemistry, 2005-09, Vol.43 (18), p.4271-4279
• Main Authors: Miura, Yutaka, Narumi, Atsushi, Matsuya, Soh, Satoh, Toshifumi, Duan, Qian, Kaga, Harumi, Kakuchi, Toyoji
• Format: Article
• Language: English
• Subjects: Applied sciences; Exact sciences and technology; living polymerization; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; radical polymerization; star polymer
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.20837

The synthesis of an AB20‐type heteroarm star polymer consisting of a polystyrene arm and 20‐arms of poly(methyl methacrylate) or poly(tert‐butyl acrylate) was carried out using the combination of nitroxide‐mediated polymerization (NMP) and atom transfer radical polymerization (ATRP). The NMP of styrene was carried out using mono‐6‐[4‐(1′‐(2″,2″,6″,6″‐tetramethyl‐1″‐piperidinyloxy)‐ethyl)benzamido]‐β‐cyclodextrin peracetate (1) to afford end‐functionalized polystyrene with an acetylated β‐cyclodextrin (β‐CyD) unit (prepolymer 2) with a number‐average molecular weight (Mn) of 11700 and a polydispersity (Mw/Mn) of 1.17. After deacetylation of prepolymer 2, the resulting polymer was reacted with 2‐bromoisobutyric anhydride to give end‐functionalized polystyrene with 20(2‐bromoisobutyrol)s β‐CyD, macroinitiator 4. The copper (I)‐mediated ATRP of methyl methacrylate (MMA) and tert‐butyl acrylate (tBA) was carried out using macroinitiator 4. The resulting polymers were isolated by SEC fractionation to produce AB20‐type star polymers with a β‐CyD‐core, 5. The well‐defined structure of 5 with weight‐average molecular weight (Mw)s of 13,500–65,300 and Mw/Mn's of 1.26–1.28 was demonstrated by SEC and light scattering measurements. The arm polymers were separated from 5 by destruction with 28 wt % sodium methoxide in order to analyze the details of their characteristic structure. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4271–4279, 2005 The synthesis of an AB20‐type heteroarm star polymer consisting of a polystyrene arm and 20‐arms of poly(methyl methacrylate) or poly(tert‐butyl acrylate) was carried out using the combination of nitroxide‐mediated polymerization and atom transfer radical polymerization. The NMP of styrene was carried out using mono‐6‐[4‐(1′‐(2″,2″,6″,6″‐tetramethyl‐1″‐piperidinyloxy)‐ethyl)benzamido]‐β‐cyclodextrin peracetate (1) to afford end‐functionalized polystyrene with an acetylated β‐cyclodextrin (β‐CyD) unit prepolymer 2 with a number‐average molecular weight (Mn) of 11,700 and a polydispersity (Mw/Mn) of 1.17. After deacetylation of prepolymer 2, the resulting polymer was reacted with 2‐bromoisobutyric anhydride to give end‐functionalized polystyrene with 20(2‐bromoisobutyrol)s β‐CyD, macroinitiator 4. The copper (I)‐mediated ATRP of methyl methacrylate and tert‐butyl acrylate was carried out using macroinitiator 4. The resulting polymers were isolated by SEC fractionation to produce AB20‐type star polymers with a β‐Cy