Cyanoxyl-mediated free-radical polymerization of acrylic acid: Its scope and limitations

Daniel Grande*, Ramiro Cuerrero, Yves Gnanou

*Corresponding author for this work

Research output: Contribution to journalReview articlepeer-review

16 Scopus citations


This work examines the scope and limitations of the cyanoxyl (OC≡N)-mediated free-radical polymerization of acrylic acid (AA) with respect to the criteria of livingness. Cyanoxyl persistent radicals were generated in situ through the reaction between arenediazonium salts (X - C 6H4N≡NBF4 Θ, where X is H, OCH3, Cl, or NO2) and sodium cyanate (NaOCN). This article thoroughly discusses the role played by such oxygen-centered radicals in the polymerization process; it particularly focuses on the influence of the concentration and nature of the diazonium salt, the solvent, and the temperature on features such as the variations of ln([M]o/[M]) versus time (where [M]0 is the initial monomer concentration and [M] is the monomer concentration), the number-average molar mass versus conversion, and the polydispersity versus conversion in cyanoxyl-mediated free-radical polymerizations of AA. Cyanoxyl-terminated samples were used as macroinitiators for the polymerization of methyl methacrylate to generate poly(acrylic acid)-b-poly(methyl methacrylate) block copolymers.

Original languageEnglish (US)
Pages (from-to)519-533
Number of pages15
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Issue number3
StatePublished - Feb 1 2005
Externally publishedYes


  • Acrylic acid
  • Cyanoxyl radicals
  • Kinetics (polym.)
  • Radical polymerization
  • Water-soluble polymers

ASJC Scopus subject areas

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry


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