Li Yang, Wang Liguo, Cao Yan, Xu Shuang, He Peng, Li Huiquan, Liu Hui
State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Energy Environmental Catalysis, College of Chemical Engineering, Beijing University of Chemical Technology Beijing 100029 China
CAS Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Clean Production Technology, Institute of Process Engineering, Chinese Academy of Sciences Beijing 100190 China
RSC Adv. 2021 Apr 15;11(23):14193-14202. doi: 10.1039/d1ra01039e. eCollection 2021 Apr 13.
A series of imidazolinium-based porous poly(ionic liquid)s (PILs) with different anions prepared by free-radical copolymerization of an arene-bridged tris-vinylimidazolium salt and divinylbenzene (DVB) were constructed. The as-prepared PILs were characterized by BET, SEM, TEM, TGA and Elemental Analysis (EA), and the results showed that they had plentiful ionic sites, and abundant and stable mesopores. In particular, the density of ionic sites and pore structure of PILs could be controlled by adjusting the content of DVB. Moreover, the PILs were used as efficient heterogeneous catalysts for the decarboxylation of cyclic carbonates to epoxides for the first time. Results showed that the catalytic activity of PILs was positively correlated with the nucleophilicity of the anions in PILs, and PDVB-[PhTVIM]Cl-1 with a chloride anion-enriched skeleton displayed the best catalytic performance. Without any solvent or cocatalyst, PDVB-[PhTVIM]Cl-1 achieved a TOF value of 108.1 h and the yield of butylene oxide of 89.6%, which was even better than the homogeneous IL-based catalysts (TOF value: 8.7 h) that had been previously reported. Meanwhile, PDVB-[PhTVIM]Cl-1 also exhibited excellent recyclability and substrate compatibility.
通过芳烃桥连的三乙烯基咪唑盐与二乙烯基苯（DVB）的自由基共聚反应，制备了一系列具有不同阴离子的咪唑啉基多孔聚离子液体（PILs）。采用BET、SEM、TEM、TGA和元素分析（EA）对所制备的PILs进行了表征，结果表明它们具有丰富的离子位点以及丰富且稳定的中孔。特别地，PILs的离子位点密度和孔结构可以通过调节DVB的含量来控制。此外，首次将PILs用作环状碳酸酯脱羧制备环氧化物的高效多相催化剂。结果表明，PILs的催化活性与PILs中阴离子的亲核性呈正相关，具有富含氯离子骨架的PDVB-[PhTVIM]Cl-1表现出最佳的催化性能。在没有任何溶剂或助催化剂的情况下，PDVB-[PhTVIM]Cl-1的TOF值达到108.
