Nishijima Ami, Ximenis Marta, Qiao Shihui, Hosono Nobuhiko, Uemura Takashi
Department of Applied Chemistry, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan.
Joxe Mari Korta Center, POLYMAT, University of the Basque Country UPV/EHU, Avda. Tolosa 72, 20018, Donostia-San Sebastian, Spain.
Chemistry. 2025 Feb 20;31(11):e202404169. doi: 10.1002/chem.202404169. Epub 2025 Jan 7.
Two-dimensional (2D) polymer network monolayers with novel block architectures were fabricated via sequential copolymerization within a pillared-layer metal-organic framework (MOF) that served as the reaction template. The MOF provides a confined 2D nanospace, restricting the crosslinking copolymerization of vinyl monomers to two dimensions. Sequential crosslinking copolymerization of methyl methacrylate and styrene, regulated by the reversible addition-fragmentation chain transfer (RAFT) process, resulted in the formation of 2D block architectures with 'patchy' domains consisting of crosslinked poly(methyl methacrylate) and polystyrene segments. Atomic force microscopy revealed that the resulting block monolayers exhibited varied morphologies on substrates, attributed to their intrinsic flexibility in 2D conformation, which facilitated microphase separation of the 2D segments within monolayers, leading to the unique aggregation morphologies. The unprecedented block topology in 2D polymeric monolayers presented in this study introduces a novel strategy for designing 2D polymeric nanomaterials with flexible yet anisotropic properties.
通过在作为反应模板的柱状层金属有机框架（MOF）内进行顺序共聚，制备了具有新型嵌段结构的二维（2D）聚合物网络单层。该MOF提供了一个受限的二维纳米空间，将乙烯基单体的交联共聚限制在二维。通过可逆加成-断裂链转移（RAFT）过程调控甲基丙烯酸甲酯和苯乙烯的顺序交联共聚，形成了具有由交联聚甲基丙烯酸甲酯和聚苯乙烯链段组成的“斑状”区域的二维嵌段结构。原子力显微镜显示，所得的嵌段单层在基底上呈现出不同的形态，这归因于它们在二维构象中的固有柔韧性，这种柔韧性促进了单层内二维链段的微相分离，从而导致独特的聚集形态。本研究中呈现的二维聚合物单层中前所未有的嵌段拓扑结构为设计具有柔性但各向异性性质的二维聚合物纳米材料引入了一种新策略。
