On the reported intermediacy of vinyl radicals in spontaneous polymerization: An ESR-spin trapping study and its significance for the bond forming initiation theory

Article abstract of DOI:10.1016/S0040-4020(97)00964-2

Deuterated isopropyl vinyl sulfides and diethyl fumarate were synthesized and employed in a re-investigation of the mechanism of initiation of spontaneous polymerization of these comonomers by means of spin- trapping/ESR spectroscopy. Previous radical spin-trapping studies had been interpreted as indicating the involvement of vinyl radicals. While our studies produced data substantially in agreement with the previous study, it must be noted that the date are not consistent with literature data for other vinyl radicals. Accordingly, results from both spin-trapping/ESR studies me inconsistent with involvement of vinyl radical intermediates, but are consistent with initiation by tetramethylene diradicals.