Designing catechol‐end functionalized poly(DMAm‐co‐NIPAM) by RAFT with tunable LCSTs

ABSTRACT Providing catechol‐end functionality to controlled structure lower critical solution temperature (LCST) copolymers is attractive, given the versatility of catechol chemistry for tethering to nanostructures. Controlled polymer chain lengths with catechol RAFT end groups are of interest to provide tunable LCST behavior to nanoparticles, although these polymerizations are relatively unexplored. Herein, the reactivity ratios for the RAFT copolymerization of N,N‐dimethylacrylamide (DMAm) and N‐isopropylacrylamide (NIPAM) pairs based on catechol‐end RAFT agents using an in situ NMR technique were first determined. Several catechol‐end poly(DMAm‐co‐NIPAM) samples were then prepared using the RAFT agent to provide copolymer. The reactivity ratios for the DMAm‐NIPAM pair were rDMAm = 1.28–1.31 and rNIPAM = 0.48–0.51. All the poly(DMAm‐co‐NIPAM) samples were found to have Mn values ≤ 26 kDa and Ð