Orthogonal Modification of Polymers via Thio-Bromo 'Click' Reaction and Supramolecular Chemistry: An Easy Method Toward Head-to-Tail Self-Assembled Supramolecular Polymers

摘要

Heterotelechelic poly(n-butyl acrylate)s (PnBuA) bearing two different and complementing supramolecular groups (namely, barbiturate (Ba) and the Hamilton wedge (HW)) at their alpha-end and omega-end (Ba-PnBuA-HW) were prepared by a combination of the reversible addition-fragmentation chain transfer (RAFT) process and the thio-bromo click reaction. The successful synthesis of the heterotelechelic H-bonding polymer Ba-PnBuA-HW (M-n,M-NMR = 7700 g/mol, M-n,M-SEC = 7500 g/mol, PDI = 1.25) was proven by a combination of H-1 NMR and MALDI-TOF mass spectrometry. Self-assembly of the resulting heterotelechelic H-bonding polymers (Ba-PnBuA-HW) in a head-to-tail fashion driven by multiple H-bondings in solution and in the bulk was proven by temperature-dependent H-1 NMR, concentration-dependent DOSY NMR studies, and rheological measurements.