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Keywords:

  • click chemistry;
  • copper-catalyzed azide–alkyne cycloaddition (CuAAC);
  • Diels–Alder;
  • graft copolymers;
  • nitroxide radical coupling (NRC);
  • poly(ε-caprolactone) (PCL);
  • poly(ethylene glycol) (PEG);
  • polyoxanorbornene (PONB);
  • polystyrene (PS);
  • triple click reactions;
  • V-shaped graft copolymers

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 α-alkyne- and α-bromide-terminated PEG (PEG-alkyne/Br) in toluene at 110 °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(ε-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. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4667–4674