One-Pot Synthesis of Star-Block Copolymers Using Double Click Reactions

Durmaz H., DAG A., HIZAL A., HIZAL G., TUNCA Ü.

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, vol.46, no.21, pp.7091-7100, 2008 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 46 Issue: 21
  • Publication Date: 2008
  • Doi Number: 10.1002/pola.23014
  • Journal Name: JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.7091-7100
  • Keywords: atom transfer radical polymerization, click reactions, Diels-Alder reaction, gel permeation chromatography (GPC), Huisgen reaction, NMR, one-pot technique, polyethers, polystyrene, star polymers, star-block copolymers, DIELS-ALDER REACTION, TRANSFER RADICAL POLYMERIZATION, H-SHAPED TERPOLYMERS, MIKTOARM STAR, POLYMERS, CHEMISTRY, COMBINATION, ATRP, POLYSTYRENE, DENDRIMERS
  • Istanbul Technical University Affiliated: Yes

Abstract

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 alpha-anthracene-omega-azide- and alpha-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 degrees 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. (C) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7091-7100, 2008