Facile access to redox responsive self-healing coating materials via living cationic block copolymerization of styrene and 2-chloroethyl vinyl ether

Poly(alkyl vinyl ether)-based functional copolymers have wide applications in many high-tech areas. However, their synthesis is still challenging which limits their applications. This article describes the synthesis of an un-precedented redox-responsive polystyrene-block-poly(2-thioethyl vinyl ether) (PSt-b-PTEVE) diblock copolymers via sequential "water tolerant" cationic polymerization of St and CEVE, followed by post-polymerization transformation of the pendant-CH2CH2Cl functionalities of PCEVE segment to -CH2CH2SH functionalities. The initiating system enabled controlled cationic polymerization of styrene (St), yielding well-defined PSt (at least up to 22500 g/mol) with relatively low dispersity (D & LE; 1.36) and polystyrene-block-poly(2-chloroethyl vinyl ether) (PSt-b-PCEVE) diblock copolymers with acceptable dispersity values (D & LE; 1.38) thereof, demonstrating high chain-end fidelity. The controlled character of the cationic polymerization reaction was confirmed by linear kinetic plots, linear increase of Mns (with low Ds) and synthesis of PSts of changing Mns simply by varying initial [St]0/[Initiator]0 feed ratio. The synthesized PSt-b-PTEVE diblock copolymers exhibited redox responsivity and self-healing behaviour. The self-healing property of the PSt-b-PTEVE diblock copolymer was studied by optical microscopy. For this, first, a mechanical cut was introduced in the cross-linked PSt-b-PTEVE thin films and then images were taken at regular intervals to investigate the healing. These promising PSt-b-PTEVE diblock co-polymers might have potential applications in many emerging areas, including functional coating.