Polymer Bulletin

, Volume 1, Issue 8, pp 529-534

First online:

A new method for investigating the mechanism of initiation of radical polymerization

  • Ezio RizzardoAffiliated withDivision of Applied Organic Chemistry, C.S.I.R.O.
  • , David H. SolomonAffiliated withDivision of Applied Organic Chemistry, C.S.I.R.O.

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The mechanism of initiation of polymerization of methyl acrylate by di-t-butyl peroxalate at 60°C, has been investigated using 2,2,6,6-tetramethylpiperidine-1-oxyl as a radical trapping agent and isolation of the resulting products. The following processes were identified: Tail addition of t-butoxy radicals to monomer, hydrogen abstraction from the methyl group of the monomer and fragmentation of the t-butoxy radicals to methyl radicals followed by tail addition of these to the methyl acrylate.