V-Shaped Graft Copolymers via Triple Click Reactions: Diels-Alder, Copper-Catalyzed Azide-Alkyne Cycloaddition, and Nitroxide Radical Coupling

Günay U. S., OZSOY B., DURMAZ H., HIZAL G., TUNCA Ü.

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, vol.51, no.21, pp.4667-4674, 2013 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 51 Issue: 21
  • Publication Date: 2013
  • Doi Number: 10.1002/pola.26888
  • Journal Name: JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.4667-4674
  • Keywords: click chemistry, copper-catalyzed azide-alkyne cycloaddition (CuAAC), Diels-Alder, graft copolymers, nitroxide radical coupling (NRC), poly(epsilon-caprolactone) (PCL), poly(ethylene glycol) (PEG), polyoxanorbornene (PONB), polystyrene (PS), triple click reactions, V-shaped graft copolymers, REACTION STRATEGIES, BLOCK-COPOLYMERS, SIDE-CHAINS, CHEMISTRY, ROMP, TERPOLYMERS, POLYMER
  • Istanbul Technical University Affiliated: Yes

Abstract

We report here a simple and universal synthetic pathway covering triple click reactions, Diels-Alder, copper-catalyzed azide-alkyne cycloaddition (CuAAC), and nitroxide radical coupling (NRC), to prepare well-defined graft copolymers with V-shaped side chains. The Diels-Alder click reaction between the furan protected-maleimide-terminated poly(ethylene glycol) (PEG) and a trifunctional core (1) carrying an anthracene, alkyne, and bromide was carried out to yield the corresponding -alkyne- and -bromide-terminated PEG (PEG-alkyne/Br) in toluene at 110 degrees C. Subsequently, the polystyrene or polyoxanorbornene with pendant azide functionality as a main backbone is reacted with the PEG-alkyne/Br and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-terminated poly(epsilon-caprolactone) using the CuAAC and NRC reactions in a one-pot fashion in N,N-dimethylformamide at room temperature to result in the target V-shaped graft copolymers. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4667-4674