One-pot synthesis of star-block copolymers using double click reactions

• Published in: Journal of polymer science. Part A, Polymer chemistry Vol. 46; no. 21; pp. 7091 - 7100
• Main Authors: Durmaz, Hakan, Dag, Aydan, Hizal, Alp, Hizal, Gurkan, Tunca, Umit
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc., A Wiley Company 01-11-2008; Wiley
• Subjects: Applied sciences; atom transfer radical polymerization; click reactions; Diels-Alder reaction; Exact sciences and technology; gel permeation chromatography (GPC); Huisgen reaction; NMR; one-pot technique; Organic polymers; Physicochemistry of polymers; polyethers; Polymerization; polystyrene; Preparation, kinetics, thermodynamics, mechanism and catalysts; star polymers; star-block copolymers; One pot reaction; 1,3-Dipolar cycloaddition; Atom transfer polymerization; Methyl methacrylate polymer; star-block copolymers; Ethylene oxide polymer; gel permeation chromatography (GPC); atom transfer radical polymerization; Styrene polymer; click reactions; polystyrene; Diels Alder addition; Ethylene oxide copolymer; Experimental study; Methyl methacrylate copolymer; Huisgen reaction; Anthracene derivatives; Star copolymer; star polymers; Monodispersed polymer; NMR; polyethers; Preparation; one-pot technique; Diels-Alder reaction; Block copolymer; Successive reaction; Styrene copolymer
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.23014

3-Arm star-block copolymers, (polystyrene-b-poly(methyl methacrylate))₃, (PS-b-PMMA)₃, and (polystyrene-b-poly(ethylene glycol))₃, (PS-b-PEG)₃, are prepared using double-click reactions: Huisgen and Diels-Alder, with a one-pot technique. PS and PMMA blocks with α-anthracene-ω-azide- and α-maleimide-end-groups, respectively, are achieved using suitable initiators in ATRP of styrene and MMA, respectively. However, PEG obtained from a commercial source is reacted with 3-acetyl-N-(2-hydroxyethyl)-7-oxabicyclo[2.2.1]hept-5-ene-2-carboxamide (7) to give furan-protected maleimide-end-functionalized PEG. Finally, PS/PMMA and PS/PEG blocks are linked efficiently with trialkyne functional linking agent 1,1,1-tris[4-(2-propynyloxy)phenyl]-ethane 2 in the presence of CuBr/N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA) at 120 °C for 48 h to give two samples of 3-arm star-block copolymers. The results of the peak splitting using a Gaussian deconvolution of the obtained GPC traces for (PS-b-PMMA)₃ and (PS-b-PEG)₃ displayed that the yields of target 3-arm star-block copolymers were found to be 88 and 82%, respectively. © Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7091-7100, 2008