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Reversible end-capping of the growing polymer chains to form dormant species (see scheme) lowers the radical concentration. Thus, cobalt(II) acetylacetonate efficiently controls the bulk radical polymerization of vinyl acetate. The molar mass of the poly(vinyl acetate) increases linearly with monomer conversion, polydispersity is as low as 1.15, and polymerization can be resumed by preformed vinyl acetate oligomers. acac=acetylacetonate.
Debuigne et al. (Tue,) studied this question.