Multiblock sequence-controlled glycopolymers via Cu(0)-LRP following efficient thiol–halogen, thiol–epoxy and CuAAC reactions

Abstract

The combination of copper(0) mediated living radical polymerization (Cu(0)-LRP) with thiol–halogen, thiol–epoxy and copper catalysed alkyne azide coupling (CuAAC) click chemistry has been employed to give a new route to multiblock sequence-controlled glycopolymers. Multiblock poly(glycidyl acrylate)-co-(acrylic acid 3-trimethylsilanyl-prop-2-ynyl ester) (poly(GA)-co-(TMSPA)) were obtained by Cu(0)-LRP in DMSO at ambient temperature via iterative monomer addition whereby the sequence of the multi blocks is attained in a designed way. Thiol–halogen and thiol–epoxy reaction of poly(GA) have been exploited, which suggested a preference for the reaction of the halogen rather than the epoxide for the thiol with triethyl amine as catalyst. The obtained multiblock poly(GA)-co-(TMSPA) were then used for sequential thiol–halogen, thiol–epoxy and CuAAC reactions to build functional glycopolymers in defined sequence.