3-miktoarm star terpolymers using triple click reactions: Diels-Alder, copper-catalyzed azide-alkyne cycloaddition, and nitroxide radical coupling reactions

Günay U. S., Durmaz H., GUNGOR E., DAG A., HIZAL G., TUNCA Ü.

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, vol.50, no.4, pp.729-735, 2012 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 50 Issue: 4
  • Publication Date: 2012
  • Doi Number: 10.1002/pola.25828
  • Journal Name: JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.729-735
  • Keywords: click reaction, copper-catalyzed azide-alkyne cycloaddition (CuAAC), Diels-Alder, miktoarm star polymer, gel permeation chromatography (GPC), NMR, nitroxide radical coupling (NRC), poly(e-caprolactone) (PCL), poly(ethylene glycol) (PEG), poly(N-butyl oxanorbornene imide) (PONB), polystyrene (PS), star polymer, triple click reactions, FRAGMENTATION CHAIN TRANSFER, ONE-POT SYNTHESIS, MACROMOLECULAR ARCHITECTURES, BLOCK-COPOLYMERS, POLYMERIZATION, CHEMISTRY, POLYMERS, SET, CU(0), GRAFT
  • Istanbul Technical University Affiliated: Yes

Abstract

Well-defined linear furan-protected maleimide-terminated poly(ethylene glycol) (PEG-MI), tetramethylpiperidine-1-oxyl-terminated poly(epsilon-caprolactone) (PCL-TEMPO), and azide-terminated polystyrene (PS-N-3) or -poly(N-butyl oxanorbornene imide) (PONB-N-3) were ligated to an orthogonally functionalized core (1) in a two-step reaction mode through triple click reactions. In a first step, DielsAlder click reaction of PEG-MI with 1 was performed in toluene at 110 degrees C for 24 h to afford alpha-alkyne-alpha-bromide-terminated PEG (PEG-alkyne/Br). As a second step, this precursor was subsequently ligated with the PCL-TEMPO and PS-N-3 or PONB-N-3 in N,N-dimethylformamide at room temperature for 12 h catalyzed by Cu(0)/Cu(I) through copper-catalyzed azide-alkyne cycloaddition and nitroxide radical coupling click reactions, yield resulting ABC miktoarm star polymers in a one-pot mode. (c) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: 729-735, 2012