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Absolute rate constants for radical-monomer reactions

The nitroxide method

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Summary

A method is described for determining the absolute rate constants for the first few propagation steps in radical polymerization. The procedure involves a product analysis of the oligomeric alkoxyamines formed when an initiator is decomposed in monomer containing a very low concentration of a nitroxide radical scavenger. The method is illustrated with analysis of data for methyl acrylate. The rate constants for the first two propagation steps for polymerization of this monomer,k p(1) andk p(2), are at least an order of magnitude greater thank p(average). Values of the absolute rate constants for reactions of phenyl and primary alkyl radicals with methyl acrylate are also estimated.

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Author notes

  1. David H. Solomon

    Present address: Department of Chemistry, University of Melbourne, 3052, Parkville, Victoria, Australia

Authors and Affiliations

  1. Division of Chemicals and Polymers, CSIRO, Private Bag 10, 3168, Clayton, Victoria, Australia

    Graeme Moad, Ezio Rizzardo & David H. Solomon

  2. Research School of Chemistry, Australian National University, 2600, Canberra, ACT, Australia

    Athelstan L. J. Beckwith

Authors
  1. Graeme Moad
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  2. Ezio Rizzardo
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  3. David H. Solomon
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  4. Athelstan L. J. Beckwith
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Moad, G., Rizzardo, E., Solomon, D.H. et al. Absolute rate constants for radical-monomer reactions. Polymer Bulletin 29, 647–652 (1992). https://doi.org/10.1007/BF01041150

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