One-Pot Synthesis of ABC Type Triblock Copolymers via a Combination of “Click Chemistry” and Atom Transfer Nitroxide Radical Coupling Chemistry

A new strategy for one-pot synthesis of ABC type triblock copolymers via a combination of “click chemistry” and atom transfer nitroxide radical coupling (ATNRC) reaction was suggested, and poly( tert -butyl acrylate)- block -polystyrene- block -poly(ethylene oxide) (P t BA−PS−PEO) and poly( tert -butyl acrylate)- block -polystyrene- block -poly(ϵ-caprolactone) (P t BA−PS−PCL) were successfully prepared by this method. The precursors with predetermined number-average molecular weight and low polydispersity indices, such as PS with α-alkyne and ω-bromine end groups, P t BA with azide end group, PEO and PCL with a 2,2,6,6-tetramethylpiperidine-1-oxyl end group, were directly prepared by living polymerization technique using the compounds with corresponding functional groups as initiators, and no further modifications of the end groups were needed, except P t BA-N 3 . The coupling reaction between precursors was carried out in the CuBr/ N,N,N ′, N ′′, N ′′-pentamethyldiethylenetriamine system with high efficiencies. The obtained polymers were characterized by FT-IR, 1 H NMR, differential scanning calorimetry, and gel permeation chromatography in detail.