Abstract
Radical additions of 2-cyano-2-propyl radicals to styrene (St), methyl methacrylate (MMA), and ethyl acrylate (EA) in the presence of large amounts of addition fragmentation chain transfer (AFCT) agent, methyl α-bromomethylacrylate (MBMA), gave low molecular weight unsaturated oligomers. The methylene protons of the ω-unsaturated end groups can be distinguished by 1H NMR spectroscopy depending on the number and the structure of the monomer units bound to the end groups. The relative amounts of oligomers containing one, two or three monomer units and the unsaturated end group were determined to evaluate the rate constants for chain transfer relative to propagation of the oligomer radicals. The rate constants for chain transfer were greater than those for propagation and the ratio of these rate constants depended on the chain length of the oligomer radical. MBMA gave its dimer together with the oligomers of St, MMA, and EA. These results confirm that propagating radicals smoothly add to MBMA to yield the adduct radical exclusively undergoing β-fragmentation and that homopropagation of MBMA is much slower than those of the monomers to function as an effective AFCT agent.
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Tanaka, K., Yamada, B. Product and Kinetic Analysis of Oligomerization by Addition-Fragmentation Chain Transfer Using Methyl α-Bromomethylacrylate. Polym J 34, 608–617 (2002). https://doi.org/10.1295/polymj.34.608
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DOI: https://doi.org/10.1295/polymj.34.608