Abstract

Abstract The first controlled free radical double ring-opening polymerization of 8,9-benzo-2-methylene-1,4,6-trioxaspiro[4,4]nonane has been achieved with tert-butyl perbenzoate as initiator in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy free radical (TEMPO) at 125 °C. Polydispersity of the polymer is significantly lower than that by the conventional radical polymerization and decreases as the concentration of TEMPO is increased. The molecular weight increases linearly with the monomer conversion.

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