State Key Laboratory of Fine Chemicals, Department of Polymer Science and Materials, School of Chemical Engineering, Dalian University of Technology, Dalian, 116024, China.
Macromol Rapid Commun. 2018 Feb;39(3). doi: 10.1002/marc.201700618. Epub 2017 Nov 17.
The motivation of this work is to build micro and mesopores within phenolic resins to extend their applications to the heterogeneous catalysis field. For this purpose, porous hyper-cross-linked phenolic resin (PFN-P) with Brunauer-Emmett-Teller (BET) surface area of 775 m g is synthesized through one-step polycondensation from tri(4-formylphenyl)phosphine and 2,5-dihydroxy-1,4-benzoquinone, which simultaneously contains abundant hydroxyl and triphenylphosphine moieties in the network. The resultant palladium-coordinated Pd@PFN-P possesses hierarchical porous structure with pore sizes ranging from 1.3 to 42.6 nm. The good hydrophilicity and broad pore sizes are advantageous for the accessibility of reactants to the catalyzing sites in the water medium for Suzuki-Miyaura reactions. As a result, high conversions for reactions between various aryl halides and phenylboronic acid are achieved under both oxygen-free and aerobic conditions. Moreover, the reaction conversions are almost unchanged after repeatedly using Pd@PFN-P for five times, showing promising potential for application in heterogeneous catalysis.
这项工作的目的是在酚醛树脂中构建微孔和介孔，将其应用扩展到多相催化领域。为此，通过三(4-醛基苯基)膦和 2,5-二羟基-1,4-苯醌的一步缩聚反应合成了具有 BET 比表面积为 775 m²/g 的多孔超交联酚醛树脂（PFN-P），该树脂网络中同时含有丰富的羟基和三苯基膦基团。得到的钯配位的 Pd@PFN-P 具有分级多孔结构，孔径范围为 1.3 至 42.6nm。良好的亲水性和较宽的孔径有利于在水介质中反应物到达催化位点，从而有利于 Suzuki-Miyaura 反应的进行。结果，在无氧和有氧条件下，各种芳基卤化物和苯硼酸之间的反应都能实现高转化率。此外，Pd@PFN-P 重复使用五次后，反应转化率几乎没有变化，在多相催化中有很好的应用前景。
