Nitroxide decomposition: Implications toward nitroxide design for applications in living free‐radical polymerization

2005/11/30 by Aaron Nilsen, Rebecca Braslau · 1 citation
Chemistry · Engineering · #Advanced Polymer Synthesis and Characterization #Fuel Cells and Related Materials #Photopolymerization techniques and applications

paper · pdf · doi:10.1002/pola.21207

openalex publication_date 2005/11/30 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/23

Abstract

Abstract Nitroxides bearing an α‐hydrogen decompose upon heating in a bimolecular reaction. A new mechanism is proposed for the decomposition of t‐butylisopropylphenyl nitroxide (TIPNO) involving the formation of a head‐to‐tail dimer, single electron transfer to form an oxammonium salt, epimerization to the corresponding nitrone, and elimination to form a conjugated oxime. This mechanism may provide insights into designing new nitroxides for use in controlled polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 697–717, 2006

Citations

• The Persistent Radical Effect: A Principle for Selective Radical Reactions and Living Radical Polymerizations
• Atom Transfer Radical Polymerization
• Unusual selectivities of radical reactions by internal suppression of fast modes
• The persistent radical effect: a prototype example of extreme, 105 to 1, product selectivity in a free-radical reaction involving persistent .cntdot.CoII[macrocycle] and alkyl free radicals
• Living Radical Polymerization by the RAFT Process
• Personal communication

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• Aminoxyl group [wikipedia]