Complex polymer architectures via RAFT polymerization: From fundamental process to extending the scope using click chemistry and nature's building blocks

Abstract Reversible addition fragmentation chain transfer (RAFT) polymerization has made a huge impact in macromolecular design. The first block copolymers were described early on, followed by star polymers and then graft polymers. In the last five years, the types of architectures available have become more and more complex. Star and graft polymers now have block structures within their branches, or a range of different branches can be found growing from one core or backbone. Even the synthesis of hyperbranched polymers can be positively influenced by RAFT polymerization, allowing end group control or control over the branching density. The creative combination of RAFT polymerization with other polymerization techniques, such as ATRP or ring-opening polymerization, has extended the array of available architectures. In addition, dendrimers were incorporated either as star core or endfunctionalities. A range of synthetic chemistry pathways have been utilized and combined with polymer chemistry, pathways such as ‘click chemistry’. These combinations have allowed the creation of novel structures. RAFT processes have been combined with natural polymers and other naturally occurring building blocks, including carbohydrates, polysaccharides, cyclodextrins, proteins and peptides. The result from the intertwining of natural and synthetic materials has resulted in the formation of hybrid biopolymers. Following these developments over the last few years, it is remarkable to see that RAFT polymerization has grown from a lab curiosity to a polymerization tool that is now been used with confidence in material design. Most of the described synthetic procedures in the literature in recent years, which incorporate RAFT polymerization, have been undertaken in order to design advanced materials.