| Abstract: | 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? C6H4N?N⊕BF , 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]0/[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. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 519–533, 2005 |
