ABCA tetrablock copolymers offer new opportunities for design of materials with novel structures. Using real-space self- consistent field theory and simulation, we systematically examined the self-assembly behavior of...ABCA tetrablock copolymers offer new opportunities for design of materials with novel structures. Using real-space self- consistent field theory and simulation, we systematically examined the self-assembly behavior of linear ABCA tetrablock copolymers in a 2D space. The simulation was carried out under conditions of symmetrical compositions and interactions. We focus on the influence of chain length ratio of block A and interactions between block A and other blocks B and C on the self-assembly behavior of the copolymer system. The simulation results show that most of the structures self-assembled by the ABCA tetrablock copolymers are centrosymmetric, such as diblock-like lameUa phase, two kinds of lameUae with beads at interface, two kinds of hierarchical lamella phase, hexagonal honeycomb-like phase, lamella phase with mixed BC and hexagonal spheres with mixed BC. Furthermore, we find that a novel noncentrosymmetric Janus spheres can be obtained when the interaction between blocks B and C is strong, whereas a noncentrosymmetric lamella phase was obtained at weak interaction between blocks B and C. Phase diagrams for the ABCA tetrablock copolymers with different interaction strength between blocks B and C are constructed by comparing free energies of candidate ordered structures. In addition, studies on the metastable behavior of the system reveal that enthalpy plays an important role in the metastable behavior of the ABCA tetrablock copolymer system. Our work can provide useful guide for structure control of such kind of tetrablock copolymers in experiments.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 National Natural Science Foundation of China(No.21474107)
文摘ABCA tetrablock copolymers offer new opportunities for design of materials with novel structures. Using real-space self- consistent field theory and simulation, we systematically examined the self-assembly behavior of linear ABCA tetrablock copolymers in a 2D space. The simulation was carried out under conditions of symmetrical compositions and interactions. We focus on the influence of chain length ratio of block A and interactions between block A and other blocks B and C on the self-assembly behavior of the copolymer system. The simulation results show that most of the structures self-assembled by the ABCA tetrablock copolymers are centrosymmetric, such as diblock-like lameUa phase, two kinds of lameUae with beads at interface, two kinds of hierarchical lamella phase, hexagonal honeycomb-like phase, lamella phase with mixed BC and hexagonal spheres with mixed BC. Furthermore, we find that a novel noncentrosymmetric Janus spheres can be obtained when the interaction between blocks B and C is strong, whereas a noncentrosymmetric lamella phase was obtained at weak interaction between blocks B and C. Phase diagrams for the ABCA tetrablock copolymers with different interaction strength between blocks B and C are constructed by comparing free energies of candidate ordered structures. In addition, studies on the metastable behavior of the system reveal that enthalpy plays an important role in the metastable behavior of the ABCA tetrablock copolymer system. Our work can provide useful guide for structure control of such kind of tetrablock copolymers in experiments.
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.
