Synthesis of hyperbranched degradable polymers by atom transfer radical (Co)polymerization of inimers with ester or disulfide groups

Degradable hyperbranched polymers with multiple alkyl halide chain ends were synthesized by the atom transfer radical polymerization of inimers containing ester (2‐(2′‐bromopropionyloxy)ethyl acrylate) or disulfide (2‐(2′‐bromoisobutyryloxy)ethyl 2′′‐methacryloyloxyethyl disulfide) groups. Both the homo‐ and copolymerizations (with styrene in the former case and methyl methacrylate in the latter) were studied. The hyperbranched polymers derived from the ester‐type inimer were hydrolytically degradable under basic conditions, whereas those derived from the disulfide‐containing inimer could be efficiently degraded in the presence of reducing agents such as tributylphosphine.