Munyentwali Alexis, Li Chunzhi, Li He, Yang Qihua
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023, P. R. China.
International College, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Chem Asian J. 2021 Aug 2;16(15):2041-2047. doi: 10.1002/asia.202100456. Epub 2021 Jun 14.
Synthesis of sulfonated porous polymers with improved hydrophobicity and stability is of extreme importance in both academic research and industrial applications. However, there is often a trade-off between acidity and surface hydrophobicity of sulfonated polymers. In this study, we report a strategy for the synthesis of sulfonated porous organic polymers (S-PT) with improved hydrophobicity via free radical polymerization method by using a rigid and large multidentate monomer, 1,3,5-tri(4-vinylphenyl)-benzene, having a hydrophobic core. The results of vapor adsorption measurement show that S-PT has more hydrophobic properties than sulfonated poly(divinylbenzene) (S-PD), attributed to the hydrophobic core of its multidentate monomer. Furthermore, the optimization of sulfonation time established a balance between surface acidity and hydrophobicity. Under optimized conditions, S-PT afforded up to 113 mmol g h TOF in the esterification of oleic acid with methanol, more active than commercial Amberlyst-15 with TOF of 15 mmol g h and Nafion NR50 with TOF of 7 mmol g h . We believe that the findings of this study will provide useful insights to advance the design and synthesis of solid acid catalysts for organic transformations.
合成具有改善的疏水性和稳定性的磺化多孔聚合物在学术研究和工业应用中都极为重要。然而，磺化聚合物的酸度和表面疏水性之间往往存在权衡。在本研究中，我们报告了一种通过自由基聚合法合成具有改善疏水性的磺化多孔有机聚合物（S-PT）的策略，该方法使用具有疏水核心的刚性多齿大单体1,3,5-三（4-乙烯基苯基）苯。蒸汽吸附测量结果表明，S-PT比磺化聚二乙烯基苯（S-PD）具有更多的疏水特性，这归因于其多齿单体的疏水核心。此外，磺化时间的优化在表面酸度和疏水性之间建立了平衡。在优化条件下，S-PT在油酸与甲醇的酯化反应中提供高达113 mmol g h的TOF，比商业Amberlyst-15（TOF为15 mmol g h）和Nafion NR50（TOF为7 mmol g h）更具活性。我们相信本研究的结果将为推进用于有机转化的固体酸催化剂的设计和合成提供有用的见解。
