Mingxin Zhang, Yuyan Lai, Mu Li, Tao Hong, Weiyu Wang, Haitao Yu, Lengwan Li, Qianjie Zhou, Yubin Ke, Xiaozhi Zhan, Tao Zhu, Caili Huang,* and Panchao Yin*
Monodispersed hairy nanocomposites system with typical 2-nm (isophthalic acid)24Cu24metal-organic polyhedron (MOP) as core protected by 24 polymer chains with controlled narrow molecular weight distribution has been experimentally probed by imaging and scattering studies for the heterogeneity of polymers in the nanocomposites and the confinement effect the MOPs imposing to anchored polymers. Typical confined-extending surrounded by one entanglement area is proposed to picture the physical states of polymer chains. This model dictates the counterintuitive thermal and rheological properties and prohibited solvent exchange properties of the nanocomposites whilst those polymer chain states are tunable and deterministic on the basis of their component inputs. Enlightened by the uncovered relationship between the basic structure and behavior of the MOP nanocomposites, a MOP-composited thermoplastic elastomer has been successfully obtained for the first time, providing practical solutions to improve the mechanical/rheological performances and processabilities of inorganic MOPs for suit practical applications, e.g. separation membranes.
我们设计了一种结构明确且规整的MOP-polymer复合的hairy NPs模型体系。通过对该类型hairy NPs在本体及溶液中的散射等手段的研究，确定了聚合物分子在MOP表面受限分布的形貌特征，进而提出了hairy NPs聚合物内层受限伸展、外层解受限舒展缠绕的双层微相结构模型；作者使用该双层微相结构模型成功解释了该类hairy NPs看似违反常识的热学和流变学现象。受启发于该外层缠绕内层受限伸展的结构特征，作者进而巧妙地设计并制备出首例MOP复合的热塑性弹性体，该方案提供了一种实用的方案用于提高MOPs的热力学和可加工性能，从而促进该类材料的实际运用（例如气体分离膜）。
Keywords: Metal-organic polyhedron nanocomposite confinement thermoplastic elastomer
文章链接：https://onlinelibrary.wiley.com/doi/abs/10.1002/ange.201909241