Rational design of a multi-in-one heterofunctional agent for versatile topological transformation of multisite multisegmented polystyrenes

Abstract

Architecture-transformable polymers can expand the family of stimuli-responsive polymers and be utilized to reveal the topology effect. Despite the tremendous progress, it remains a great challenge to achieve single polymer based on-demand topological transformations with reduced, similar and enhanced molar masses. To address this challenge, an initiating, coupling and pH/thermo-labile agent is designed to synthesize linker-reactive multisite multisegmented polymers (LMMPs) via tandem ATRP and ATRC, followed by intermolecular anthracene dimerization to generate single-chain folding polystyrenes. Meanwhile, bromine and hydroxyl groups are incorporated into each linker to generate graft copolymers comprising poly(tert-butyl acrylate) and poly(ε-caprolactone) side chains. The self-immolative tertiary amine ester linker allows thermo-triggered topological transformation from multisegmented, intrachain folding and graft polymers to one-segment polymers. The robust one-shot strategy can afford a promising platform to construct heterofunctional multisegmented polymers with tailor-made structures and functions.