One-pot preparation of 3-miktoarm star terpolyrmers via click [3+2] reaction

Altintas O., Yankul B., Hizal G., Tunca U.

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, vol.45, no.16, pp.3588-3598, 2007 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 45 Issue: 16
  • Publication Date: 2007
  • Doi Number: 10.1002/pola.22108
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.3588-3598
  • Keywords: atom transfer radical polymerization, [3+2] click reaction, Differential Scanning Calorimetry (DSC), gel permeation chromatography (GPC), miktoarm star terpolymers, nitroxide mediated radical polymerization, one-pot technique, ring opening polymerization, star polymers, TRANSFER RADICAL POLYMERIZATION, DIELS-ALDER REACTION, RING-OPENING POLYMERIZATION, H-SHAPED TERPOLYMERS, MIKTOARM STAR, BLOCK-COPOLYMERS, EFFICIENT ROUTE, POLYMERS, COMBINATION, CHEMISTRY
  • Istanbul Technical University Affiliated: Yes


The preparation of 3-miktoarm star terpolymers using nitroxide mediated radical polymerization (NMP), ring opening polymerization (ROP), and click reaction [3 + 2] are carried out by applying two types of one-pot technique. In the first one-pot technique, NMP of styrene (St), ROP of epsilon-caprolactone (epsilon-CL), and [3 + 2] click reaction (between azide end-functionalized poly(ethylene glycol) (PEG-N-3)/or azide end-functionalized poly(methyl methacrylate) (PMMA-N-3) and alkyne) are carried out in the presence of 2-(hydroxymethyl)-2-methyl-3-oxo-3-(2-phenyl-2-(2,2,6,6-tetramethylpiperidin-1-yloxy)ethoxy) propyl pent-4-ynoate, 2, as an initiator for 48 h at 125 degrees C (one-pot/one-step). As a second technique, NMP of St and ROP of epsilon-CL were conducted using 2 as an initiator for 20 h at 125 degrees C, and subsequently PEG-N-3 or azide end-functionalized poly(tert-butyl acrylate (PtBA-N-3) was added to the polymerization mixture, followed by a click reaction [3 + 2] for 24 h at room temperature (one-pot/two-step). The 3-miktoarm star terpolymers, PEG-poly(epsilon-caprolactone)(PCL)-PS, PtBA-PCL-PS and PMMA-PCL-PS, were recovered by a simple precipitation in methanol without further purification. (C) 2007 Wiley Periodicals, Inc.