Synthesis of diverse α,ω-telechelic polystyrenes with di- and tri-functionality via tandem or one-pot strategies combining aminolysis of RAFT-polystyrene and a thiol–ene “click” reaction

Abstract

A thiol–ene “click” reaction proceeds with facile reaction conditions for complete conversion, and displays a higher tolerance to various backbones and functional groups compared with traditional coupling and functionalization strategies. Herein, well-defined α,ω-telechelic polystyrenes with trithiocarbonate and carboxyl terminal groups (PS-CTA) were firstly synthesized via reversible addition-fragmentation chain transfer (RAFT) radical polymerization. Then, the terminal thiol group was converted from the thiocarbonylthio end group of PS-CTA and subsequently reacted with n-butyl acrylate and vinyl ferrocene, respectively, through thiol–ene “click” chemistry, to achieve α,ω-telechelic polystyrenes with difunctionality. Alternatively, a facile one-pot simultaneous aminolysis and thiol–ene “click” reaction using PS-CTA and various ene-bearing compounds as reactants was found to have high efficiency in synthesizing diverse α,ω-telechelic polystyrenes with di- and tri-functionality. Various functional groups such as hydroxyl, acrylate, fluorinated acrylate, ferrocene and allyl, etc. can be successfully incorporated as terminal groups of α,ω-telechelic polystyrenes.