Summary
A new dissociative mechanism involving enolate anion intermediates is proposed for the process currently categorized as nucleophile-catalyzed “group transfer polymerization” (GTP). A rapid, reversible complexation of small concentrations of enolate anions with silyl ketene acetals (reversible termination) is proposed to explain the living nature of these polymerizations and the role of the silyl ketene acetals in “GTP”. It is proposed that these polymerizations do not involve “group transfer” in the chain-propagating step. These mechanistic conclusions are based on studies of the tetrabutylammonium 9-methyl-fluorenide- and methyllithium-initiated polymerizations of methyl methacrylate at ambient temperatures in the presence and absence of silyl ketene acetal.
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Quirk, R.P., Bidinger, G.P. Mechanistic role of enolate ions in “group transfer polymerization”. Polymer Bulletin 22, 63–70 (1989). https://doi.org/10.1007/BF00283285
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DOI: https://doi.org/10.1007/BF00283285