Facile synthesis of thermoresponsive block copolymers of N-isopropylacrylamide using heterogeneous controlled/living nitroxide-mediated polymerizations in supercritical carbon dioxide

Padraig O'Connor, Rongbing Yang, William M. Carroll, Yury Rochev, Fawaz Aldabbagh

Research output: Contribution to a Journal (Peer & Non Peer)Articlepeer-review

23 Citations (Scopus)

Abstract

A new protocol for preparation of thermoresponsive poly(N- isopropylacrylamide, NIPAM) containing block copolymers is described. It involves two successive heterogeneous controlled/living nitroxide-mediated polymerizations (NMPs) in supercritical carbon dioxide (scCO 2) using N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)]nitroxide (SG1), as the nitroxide. Precipitation NMPs give narrow dispersity macroinitiators (MIs), and a first report of the controlled/living polymerization of N,N-dimethylacrylamide (DMA) in scCO 2 is described. The MI is then used in an inverse suspension NMP of NIPAM in scCO 2 resulting in the efficient preparation of block copolymers containing DMA, tert-butyl acrylate and styrene. Aqueous cloud point temperature analysis for poly(DMA)-b-poly(NIPAM) and poly(acrylic acid)-b-poly(NIPAM) shows a significant dependence on poly(NIPAM) chain length for a given AB block copolymer.

Original languageEnglish
Pages (from-to)1279-1288
Number of pages10
JournalEuropean Polymer Journal
Volume48
Issue number7
DOIs
Publication statusPublished - Jul 2012

Keywords

  • Macroinitiator
  • Polymer
  • Precipitation polymerisation
  • Radical
  • Reversible-deactivation
  • Suspension polymerisation

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