The role of mid-chain radicals in acrylate free radical polymerization: Branching and scission

Thomas Junkers, Christopher Barner-Kowollik

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176 Citations (Scopus)


The past 5 years have seen a significant increase in the understanding of the fate of so-called mid-chain radicals (MCR), which are formed during the free radical polymerization of monomers that form highly reactive propagating radicals and contain an easily abstractable hydrogen atom. Among these monomers, acrylates are, beside ethylene, among the most promi-nent. Typically, a secondary propagating acrylate-type macro-radical (SPR) can easily transfer its radical functionality via a six-membered transition state to a position within the polymer chain (in a so-called backbiting reaction), creating a tertiary MCR. Alternatively, the radical function can be transferred intramolecularly to any position within the chain (also forming an MCR) or intermolecularly to another polymer strand. This article aims at providing a comprehensive overview of the up-to-date knowledge about the rates at which MCRs are formed, their secondary reactions as well as the consequences of their occurrence under variable reaction conditions. We explore the latest aspects of their detection (via electron spin resonance spectroscopy) as well as the characterization of the polymer structures to which they lead (via high resolution mass spectrometry). The presence of MCRs leads to the formation of branched polymers and the partial formation of polymer networks. They also limit the measurement of kinetic parameters (such as the SPR propagation rate coefficient) with conventional methods. However, their occurrence can also be used as a synthetic handle, for example, the high-temperature preparation of macromonomers.

Original languageEnglish
Pages (from-to)7585-7605
Number of pages21
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Issue number23
Publication statusPublished - 1 Dec 2008
Externally publishedYes


  • β-scission
  • Acrylates
  • Electron spin resonance spectroscopy
  • Free radical polymerization
  • Kinetics (polym.)
  • Mass spectrometry
  • Microstructure
  • Mid-chain radicals
  • Transfer reactions

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