Cao Qingbin, Zhang Shaowen, Zhang Li, Gao Fei, Chen Jupeng, Dong Yuping, Li Xiaofang
Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, 5 South Zhongguancun Street, Haidian District, Beijing 100081, China.
Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China.
ACS Appl Mater Interfaces. 2021 Mar 24;13(11):13693-13704. doi: 10.1021/acsami.1c00512. Epub 2021 Mar 12.
Covalent organic frameworks (COFs) are applied widely in organic catalysis; however, no precedent has been reported in polymerization catalysis. Herein, we report the new application of COFs for polymerization catalysis. Different amounts of homogeneous Rh catalyst are incorporated into the COF via post-treatment to give a series of TPB-DMTP-COF-X wt % Rh (-) containing varying amounts of Rh from 2.74 to 11.38 wt %. In contrast to the known Rh catalysts, TPB-DMTP-COF-X wt % Rh (-) display an uncommon synergistic effect and exceptional steric confinement effect of nanochannels. Therefore, they possess the advantages of both homogeneous catalysts in high activity and selectivity and heterogeneous catalysts in stability and recyclability with extremely high activity up to 1.3 × 10 g·mol·h and -selectivity up to 99% and can be readily recycled and reused five times in the polymerization of phenylacetylene and its derivatives, affording polyphenylacetylene and its derivatives having helical structures, aggregation-induced emission properties, or fluorescence properties with narrow molecular weight distributions.
共价有机框架（COFs）在有机催化中有着广泛应用；然而，在聚合催化方面尚无先例报道。在此，我们报告了COFs在聚合催化中的新应用。通过后处理将不同量的均相铑催化剂引入到COF中，得到一系列含铑量从2.74 wt%到11.38 wt%不等的TPB-DMTP-COF-X wt% Rh（-）。与已知的铑催化剂不同，TPB-DMTP-COF-X wt% Rh（-）表现出罕见的协同效应和纳米通道独特的空间限制效应。因此，它们兼具均相催化剂高活性和高选择性以及多相催化剂稳定性和可回收性的优点，在苯乙炔及其衍生物的聚合反应中活性极高，可达1.3×10 g·mol·h，选择性高达99%，并且可以很容易地回收再利用五次，得到具有螺旋结构、聚集诱导发光性质或荧光性质且分子量分布窄的聚苯乙炔及其衍生物。
