CHAPTER 2: Direct Synthesis of Glycopolymers Using Glycomonomers

This chapter reviews the direct synthesis of glycopolymers using glycomonomers with a focus on the developments in the last few years. A short history of the synthesis of glycopolymers is presented, which outlines the main developments from the first report of glycopolymers to the introduction of various polymerization techniques. This is followed by an overview of synthetic routes to prepare glycomonomers for use in various polymerization techniques. Finally, the synthesis of glycopolymers is discussed, starting with radical techniques such as free radical polymerization and the various reversible-deactivation radical polymerization processes [nitroxide-mediated polymerization (NMP), atom-transfer polymerization (ATRP) and its related techniques, cyanoxyl-mediated polymerization and reversible addition fragmentation chain transfer (RAFT) polymerization], followed by ionic polymerization, ring-opening metathesis polymerization (ROMP) and ionic ring-opening polymerization. Radical polymerization, via either conventional or reversible-deactivation radical polymerization, is still the most commonly used pathway to glycopolymers. It is also highlighted that some techniques such as anionic polymerization, cationic polymerization and ROMP have been neglected over the last few years whereas ionic ring-opening polymerization still attracts some interest, probably owing to the possibility of generating degradable polymers.