The exploitation of new green polymerization avenues for the effective synthesis of polymers by reversible-deactivation radical polymerization plays a critical role in pursuing the development of polymeric materials.I...The exploitation of new green polymerization avenues for the effective synthesis of polymers by reversible-deactivation radical polymerization plays a critical role in pursuing the development of polymeric materials.In this work,serials of deep eutectic solvents(DES)with intermolecular-hydrogen-bonding interaction were constructed as catalysts and medium for actuating reversible complexation-mediated polymerization(RCMP)for the first time,yielding methacrylate polymers with high monomer conversion and narrow dispersion molecular weight in both water and oil systems.The mechanism and elementary reaction of RCMP were explored deeply,revealing that the complexation of initiator with DES to generate radicals was a ratecontrolling step and intermolecular-hydrogen-bond was primary factor to influence polymerization rate.Moreover,the insights of density functional theory calculations revealed that negative electrostatic potential ensured nucleophilic capacity.This investigation demonstrated the considerable potential of DES for RCMP,which is anticipated for other polymerization applications as a novel medium mode.展开更多
Vesicles obtained by the self-assembly of asymmetric tetrablock copolymers are a class of materials with fascinating properties.However,simple strategies to synthesize asymmetric tetrablock copolymers are limited.Here...Vesicles obtained by the self-assembly of asymmetric tetrablock copolymers are a class of materials with fascinating properties.However,simple strategies to synthesize asymmetric tetrablock copolymers are limited.Herein,we have designed and synthesized an initiator which generates radicals by either heating or photoirradiation.Taking the advantages of organocatalyzed reversible complexation mediated radical polymerization which has lower energy requirements,milder reaction conditions,and reduced generation of hazardous byproducts,a three steps synthetic route following“photo-photo-thermal”initiation condition for the preparation of asymmetric CABC tetrablock copolymers with controllable molecular weight,precise block composition and low polydispersity was developed.展开更多
基金financially supported by the State Key Program of National Natural Science Foundation of China(U21A20313)the Key Program of Qingyuan Innovation Laboratory(00221003)+2 种基金the“111”Program of Fuzhou Universitythe Natural Science Foundation of Fujian Province(2019J05040)the China Postdoctoral Science Foundation(2022M20739)。
文摘The exploitation of new green polymerization avenues for the effective synthesis of polymers by reversible-deactivation radical polymerization plays a critical role in pursuing the development of polymeric materials.In this work,serials of deep eutectic solvents(DES)with intermolecular-hydrogen-bonding interaction were constructed as catalysts and medium for actuating reversible complexation-mediated polymerization(RCMP)for the first time,yielding methacrylate polymers with high monomer conversion and narrow dispersion molecular weight in both water and oil systems.The mechanism and elementary reaction of RCMP were explored deeply,revealing that the complexation of initiator with DES to generate radicals was a ratecontrolling step and intermolecular-hydrogen-bond was primary factor to influence polymerization rate.Moreover,the insights of density functional theory calculations revealed that negative electrostatic potential ensured nucleophilic capacity.This investigation demonstrated the considerable potential of DES for RCMP,which is anticipated for other polymerization applications as a novel medium mode.
基金supported by the National Natural Science Foundation of China(No.U21A20313)the Natural Science Foundation of Fujian Province(No.2023J01265)+1 种基金the Key Program of Qingyuan Innovation Laboratory(No.00221003)the‘111’program of Fuzhou University。
文摘Vesicles obtained by the self-assembly of asymmetric tetrablock copolymers are a class of materials with fascinating properties.However,simple strategies to synthesize asymmetric tetrablock copolymers are limited.Herein,we have designed and synthesized an initiator which generates radicals by either heating or photoirradiation.Taking the advantages of organocatalyzed reversible complexation mediated radical polymerization which has lower energy requirements,milder reaction conditions,and reduced generation of hazardous byproducts,a three steps synthetic route following“photo-photo-thermal”initiation condition for the preparation of asymmetric CABC tetrablock copolymers with controllable molecular weight,precise block composition and low polydispersity was developed.
