Synthesis of multisegmented degradable polymers by atom transfer radical cross-coupling

Multisegmented degradable polymers were successfully synthesized via atom transfer radical cross-coupling of alpha,omega-dihalogenated polymers prepared by atom transfer radical polymerization with dinitroxides. High molecular weight polymers (M-n > 100 000 g mol(-1)) with more than 10 cleavable units in the main chain were prepared. These multisegmented polymers were chemically and thermally degraded. Chemical degradation, via basic hydrolysis or disulfide reduction, as well as thermal degradation, by heating in the presence or in the absence of free nitroxides, led to low molecular weight polymers with relatively low polydispersity (2100 g mol(-1)<= M-n <= 15 100 g mol(-1); 1.08 <= M-w/M-n <= 1.46).