Abstract

Poly(alkyl vinyl ether)-containing multifunctional block copolymers (BCPs) are challenging to synthesize and still limited in numbers despite their possible applications in high-tech areas. This article presents the synthesis of unprecedented amphiphilic poly(2-thioethyl vinyl ether)-block-poly(poly(ethylene glycol) methacrylate) (PTEVE-b-PPEGMA) BCPs via sequential ionic liquid-mediated cationic polymerization of CEVE and recyclable alloy-mediated photoRDRP of PEGMA, followed by post-polymerization modification of the pendant -CH2CH2Cl functionality to -CH2CH2SH. Controlled nature of both the cationic polymerization and photoRDRP was demonstrated by the first-order kinetic and linear increase of molecular weight with increase of monomer conversion, keeping low dispersity values. The synthesized PTEVE-b-PPEGMA BCP exhibited a dual (redox and temperature) stimuli-response. The cloud point of PTEVE-b-PPEGMA BCP can be tuned by changing the PEGMA mol% in the BCP. Amphiphilic PTEVE-b-PPEGMA diblock copolymer undergoes self-aggregation forming spherical nano-objects. These promising PTEVE-b-PPEGMA diblock copolymers could be used for many applications, including dual stimuli-responsive materials, materials with tunable hydrophobicity, and contaminant removal.

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