Linear Tetrablock Quaterpolymers via Triple Click Reactions, Azide-Alkyne, Diels-Alder, and Nitroxide Radical Coupling in a One-Pot Fashion

Durmaz H. , Hızal G. , Tunca Ü.

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, vol.49, no.9, pp.1962-1968, 2011 (Journal Indexed in SCI) identifier identifier

  • Publication Type: Article / Article
  • Volume: 49 Issue: 9
  • Publication Date: 2011
  • Doi Number: 10.1002/pola.24622
  • Page Numbers: pp.1962-1968
  • Keywords: atom transfer radical polymerization (ATRP), azide-alkyne cycloaddition reaction, block copolymer, click reactions, Diels-Alder cycloaddition reaction, GPC, nitroxide radical coupling reaction, NMR, poly(ethylene glycol), polystyrene, poly(tert-butyl acrylate), poly(n-butyl acrylate), poly(epsilon-caprolactone), quaterpolymer, ring opening polymerization (ROP), DEFINED BLOCK-COPOLYMERS, SET-LRP, FUNCTIONALIZED POLYMERS, TRIBLOCK COPOLYMERS, MATERIALS SCIENCE, MODULAR SYNTHESIS, GRAFT-COPOLYMERS, STAR POLYMERS, CHEMISTRY, POLYMERIZATION


Azide-alkyne and Diels-Alder click reactions together with a click-like nitroxide radical coupling reaction were used in a one-pot fashion to generate tetrablock quaterpolymer. The various living polymerization generated linear polymers with orthogonal end-functionalities, maleimide-terminated poly(ethylene glycol) (PEG-MI), anthracene-and azide-terminated polystyrene, alkyne- and bromide-terminated poly(tert-butyl acrylate) or alkyne-poly(n-butyl acrylate), and tetramethylpiperidine-1-oxyl (TEMPO)-terminated poly(epsilon-caprolactone) (PCL-TEMPO) were clicked together in a one-pot fashion to generate PEG-b-PS-b-PtBA- b-PCL or PEG-b-PS-b-PnBA-b-PCL quaterpolymer using Cu(0), CuBr, and N, N, N, N '', N ''-pentamethyldiethylenetriamine as catalyst in dimethyl formamide at 80 degrees C for 36 h. Linear precursors and target quaterpolymers were analyzed via H-1 NMR and gel permeation chromatography. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 1962-1968, 2011