• atom transfer radical polymerization;
  • block copolymers;
  • graft copolymers;
  • “click” chemistry;
  • atom transfer nitroxide radical coupling


A new strategy for the one-pot preparation of ABA-type block-graft copolymers via a combination of Cu-catalyzed azide-alkyne cycloaddition (CuAAC) “click” chemistry with atom transfer nitroxide radical coupling (ATNRC) reaction was reported. First, sequential ring-opening polymerization of 4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl (GTEMPO) and 1-ethoxyethyl glycidyl ether provided a backbone with pendant TEMPO and ethoxyethyl-protected hydroxyl groups, the hydroxyl groups could be recovered by hydrolysis and then esterified with 2-bromoisobutyryl bromide, the bromide groups were converted into azide groups via treatment with NaN3. Subsequently, bromine-containing poly(tert-butyl acrylate) (PtBA-Br) was synthesized by atom transfer radical polymerization. Alkyne-containing polystyrene (PS-alkyne) was prepared by capping polystyryl-lithium with ethylene oxide and subsequent modification by propargyl bromide. Finally, the CuAAC and ATNRC reaction proceeded simultaneously between backbone and PtBA-Br, PS-alkyne. The effects of catalyst systems on one-pot reaction were discussed. The block-graft copolymers and intermediates were characterized by size-exclusion chromatography, 1H NMR, and FT-IR in detail. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010