Synthesis of semifluorinated block copolymers by atom transfer radical polymerization

Karunakaran Radhakrishnan, Karen A. Switek, Marc A. Hillmyer

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31 Scopus citations


Two sets of styrene-based semifluorinated block copolymers, one with a perfluoroether pendant group and another with a perfluoroalkyl group, were synthesized by atom transfer radical polymerization. Microphase separation of the block copolymers was established by small-angle X-ray scattering and differential scanning calorimetry (DSC). DSC measurements also showed that the perfluoroether-based polymer had a low glass-transition temperature (-44°C). Contact-angle measurements indicated that the semifluorinated block copolymers had low surface energies (ca. 13 mJ/m2). These materials hold promise as low-surface-energy additives or surfactants for supercritical CO2 applications.

Original languageEnglish (US)
Pages (from-to)853-861
Number of pages9
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Issue number4
StatePublished - Feb 15 2004


  • Atom transfer radical polymerization (ATRP)
  • Block copolymers
  • Polystyrene
  • Self-assembly
  • Semifluorinated


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