Free Radical Polymers with Tunable and Selective Bio- and Chemical Degradability

摘要

A versatile synthetic strategy has been developed which enables the facile incorporation of cleavable functional groups, i.e. esters, thioesters and disulfides, into the carbon-carbon backbone of vinyl-based polymers. Through the synthesis of novel cyclic monomers, RAFT-mediated radical ring-opening copolymerizations with traditional vinyl monomers such as methyl methacrylate, N,N-dimethylaminoethyl methacrylate and 2-hydroxyethyl methacrylate leads to the introduction of controlled degradability into these widely used vinyl copolymer systems. An additional benefit of this strategy is the inherent versatility available through the incorporation of cyclic monomers containing diverse functional groups such as esters, thioesters, disulfides and silyl ether units that allow degradation under basic/acidic, reductive or enzymatic conditions. By integrating multiple, orthogonal cyclic monomers into linear copolymer backbones, well-defined systems with programmable degradation profiles are obtained which allows for tunable, selective and step-wise degradation of the vinyl polymer backbones.