Aqueous RAFT polymerization: Recent developments in synthesis of functional water-soluble (Co)polymers with controlled structures

Reversible addition-fragmentation chain transfer (RAFT) polymerization has been the focus of intensive research over the past few years since this methodology allows the synthetic tailoring of macromolecules with complex architectures including block, graft, comb, and star structures with predetermined molecular weight, terminal functionality, and narrow molecular weight distribution. In this paper we recount significant milestones in achieving controlled free radical homopolymerization and block copolymerization of water-soluble and amphiphilic monomers including nonionic, cationic, anionic, and zwitterionic species. It is shown that under aqueous conditions, control of homopolymerization and further blocking to extend the molecular weight or to produce precisely structured block copolymers require not only careful selection of reagents (initiator, chain transfer agent, and monomer) but also regulation or elimination of hydrolysis of the omega-terminal thiocarbonylthio functionality. The technological potential of such systems is illustrated for the stimuli (pH) reversible micellization of amphiphilic block copolymers and for stabilization and stimuli responsive aggregation of gold nanoparticles hearing covalently tethered co(polymers). Given the advantages of RAFT over other controlled free radical techniques for preparation of water-soluble architectures, it may be anticipated that this technology will be at the forefront of nano- and microscale self-assembly in electronics and biotechnology.