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EPR Analysis of n-Butyl Acrylate Radical Polymerization

✍ Scribed by Johannes Barth; Michael Buback; Pascal Hesse; Tatiana Sergeeva

Publisher: John Wiley and Sons
Year: 2009
Tongue: English
Weight: 322 KB
Volume: 30
Category: Article
ISSN: 1022-1336
DOI: 10.1002/marc.200900531

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✦ Synopsis

Abstract

Via electron paramagnetic resonance (EPR) spectroscopy, concentrations of secondary propagating radicals (SPRs) and tertiary mid‐chain radicals (MCRs) in n‐butyl acrylate solution polymerization were measured. The EPR spectrum is dominated by the 4‐line spectrum of SPRs at −50 °C and by the 7‐line spectrum of MCRs at +70 °C. At intermediate temperatures, a third spectral component is seen, which is assigned to an MCR species with restricted rotational mobility. The MCR components are produced by 1,5‐hydrogen shift (backbiting) of SPRs. The measured ratio of MCRs to SPRs allows for estimating the rate coefficient k for monomer addition to a mid‐chain radical. For 70 °C, k is obtained to be 65.5 L · mol^−1^ · s^−1^.

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