Fast track access to multi-block copolymers via thiol-bromo click reaction of telechelic dibromo polymers

Multi-block copolymers offer a plethora of exciting properties, easily tuned by modulating parameters such as monomer composition, block length, block number and dispersity. Here, we demonstrate a highly efficient one-pot synthesis of such materials by combining copper-mediated reversible-deactivation radical polymerisation (Cu-RDRP) with thiol-bromo post-polymerisation modification. Specifically, the use of bifunctional bromo initiators and bisthiol compounds furnishes hydrophilic, hydrophobic and amphiphilic architectures in less than 10 minutes via a step growth-type mechanism. Furthermore, the degradation characteristics of the obtained polymers are demonstrated in oxidative, methylating and high temperature environments. The rate of degradation and nature of the end-group is shown to vary with the choice of bisthiol linker and other reaction conditions.