上海科技大学李涛团队报道了利用配位交联表面改性方法实现理想金属有机骨架粒子在聚合物基体中的分散性。 相关研究成果发表在2021年4月15日出版的国际知名学术期刊《德国应用化学》。

根据“相似相溶”的机理，提高金属有机骨架（MOF）粒子在聚合物基体中的分散性的最佳方法是用与基体相同的聚合物对MOF表面进行改性。

该研究工作首次描述了用聚酰亚胺、聚砜、聚碳酸酯和具有固有微孔1（PIM-1）的聚合物修饰各种MOF表面的通用方法。该方法首先利用静电吸附快速修饰带正电荷的MOF表面，形成一层带负电荷的金属-有机纳米胶囊PgC5Cu。与聚合物混合后，PgC5Cu上的铜在热活化时开放金属位点可以协调地交叉连接聚合物表面的极性官能团，从而导致均匀的亚10 nm聚合物涂层的固定化。

研究人员定量分析了MOF粒子间自由程间距的分布，结果表明，当表面聚合物与基体聚合物相匹配时，MOF的分散性不仅在视觉上得到了改善，而且与理论上预测的理想分散模型完全吻合，且其中不存在聚集驱动力。

附：英文原文

Title: Coating the Right Polymer: Achieving Ideal Metal‐Organic Framework Particle Dispersibility in Polymer Matrixes Using a Coordinative Crosslinking Surface Modification Method.

Author: Conger Li, Junhong Liu, Kexin Zhang, Songwei Zhang, Yongjin Lee, Tao Li

Issue&Volume: 2021-04-15

Abstract: According to the rule “like dissolves like”, the best way to improve the dispersibility of metal‐organic framework (MOF) particles in a polymer matrix is to modify the MOF surface with the same polymer as the matrix. This work describes the first generalizable method to modify various MOF surfaces with polyimide, polysulfone, polycarbonate, and polymer of intrinsic microporosity‐1 (PIM‐1). The method first utilizes electrostatic adsorption to rapidly decorate positively charged MOF surfaces with a layer of negatively charged metal‐organic nanocapsule, PgC  5  Cu.  After mixing with the polymer, the copper open metal sites on PgC  5  Cu can coordinatively cross‐link the polar functional groups on the surface polymer upon thermal activation thereby resulting in the immobilization of a uniform sub‐10 nm polymer coating.  We quantitatively analyzed the distribution of free path spacing between MOF particles and demonstrated that when the surface polymer matches the matrix polymer, the MOF dispersion was not only visually improved but also found to align perfectly with a theoretically predicted ideal dispersion model where no aggregation driving force was present.

DOI: 10.1002/anie.202104487

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202104487