Wang Xiaochen, Zhou Yu, Guo Zengjing, Chen Guojian, Li Jing, Shi Yuming, Liu Yangqing, Wang Jun
State Key Laboratory of Materials-Oriented Chemical Engineering , College of Chemistry and Chemical Engineering , Nanjing Tech University (former Nanjing University of Technology) , Nanjing , Jiangsu 210009 , P. R. China . Email:
Chem Sci. 2015 Dec 1;6(12):6916-6924. doi: 10.1039/c5sc02050f. Epub 2015 Aug 27.
Meso-macroporous hierarchical poly(ionic liquid)s (MPILs) with extremely high ionic site densities and tunable pore structures were ionothermally synthesized through the free radical self-polymerization of our newly designed rigid bis-vinylimidazolium salt monomer. The synthesis avoided the use of any templates, gave a high yield (>99%) and allowed recycling of the IL solvent; thus it is facile, atom-efficient, environmentally friendly and sustainable. The synthesized MPILs possessed distinctive features of polycation matrices, abundant halogen anions, and large surface areas. They not only presented enhanced CO capture, but led to breakthroughs in the heterogeneous catalytic conversion of CO into cyclic carbonates: (1) unprecedented high activity at atmospheric pressure and low temperature; (2) good substrate compatibility, even being active towards the extremely inert aliphatic long carbon-chain alkyl epoxides. This result renders the first occasion of a metal-solvent-additive free recyclable heterogeneous cycloaddition of CO at such mild conditions.
通过我们新设计的刚性双乙烯基咪唑鎓盐单体的自由基自聚合反应，离子热合成了具有极高离子位点密度和可调孔结构的介孔-大孔分级聚离子液体（MPILs）。该合成方法避免了使用任何模板，产率高（>99%），且离子液体溶剂可循环使用；因此，它简便、原子经济、环境友好且可持续。合成的MPILs具有聚阳离子基质、丰富的卤素阴离子和大表面积的独特特征。它们不仅提高了对CO的捕获能力，还在将CO非均相催化转化为环状碳酸酯方面取得了突破：（1）在常压和低温下具有前所未有的高活性；（2）良好的底物兼容性，甚至对极其惰性的脂肪族长碳链烷基环氧化物也有活性。这一结果首次实现了在如此温和条件下无金属-溶剂-添加剂的可循环非均相CO环加成反应。
