Low temperature RAFT/MADIX gel polymerisation: access to controlled ultra-high molar mass polyacrylamides

We pushed back the limits of molar mass control in aqueous RAFT/MADIX polymerisation through a fast and quantitative gel polymerisation of a series of acrylamido monomers. Unprecedentedly high Mn up to 106 g mol−1 with low dispersities (Đ < 1.2) was achieved in homopolymerisation, statistical and block copolymerisation of a selection of acrylamido monomers such as AM, DMA, AMPS and NIPAM. The reasons for access to an abnormally high kinetic chain length in the presence of a RAFT/MADIX agent are discussed.