Facile synthesis of gradient copolymers enabled by droplet-flow photo-controlled reversible deactiva

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Monomer sequence influences the properties and applications of polymers.Consequently,massive efforts have been made to implement sequence control of polymers.In this work,we developed a computer-aided droplet-flow polymerization based on photo-controlled reversible-deactivation radical polymerization (photo-RDRP),enabling synthesis of gradient copolymers of tunable sequential arrangements,low dispersity and good structural fidelity from various monomers without following their intrinsic reactivities,which is a key limitation in sequence control.The obtained gradient copolymers exhibit unique thermal properties and stimulus responsiveness comparing with the random and block counterparts,and their glass transition behaviour could be regulated by the gradient tendency.We believe that the unprecedented gradient photo-RDRP based on flow synthesis opens a robust and versatile avenue to streamline the synthesis of well-defined gradient polymers,and is compatible with other polymerization mechanisms.
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