Controlled radical double ring‐opening polymerization of 2‐methylene‐1,4,6‐trioxaspiro[4,4]nonane

Controlled radical double ring‐opening polymerization of 2‐methylene‐1,4,6‐trioxaspiro[4,4]nonane (MTN) has been achieved with tert‐butyl perbenzoate (TBPB) as initiator in the presence of 2,2,6,6‐tetramethyl‐1‐piperidinyloxy free radical (TEMPO) at 125 °C. The molecular weight polydispersity of the polymers is obviously lower than that of polymers obtained by conventional procedures. As the [TEMPO]/[TBPB] molar ratio increased, the polydispersity decreased and a polydisperty as low as 1.2 was obtained at high TEMPO concentration. With the conversion of the monomer increasing, the molecular weight of the polymers turned higher and a linear relationship between the M_w and the monomer conversion was observed. The monomer conversion, however, did not exceed 30 %. © 2000 Society of Chemical Industry