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多孔聚离子液体催化二氧化碳辅助环氧乙烷水合反应

洪扬,李丹丹,张景顺,章子旺,高国华   

  1. 华东师范大学
  • 收稿日期:2024-12-30 修回日期:2025-03-18 出版日期:2025-03-24 发布日期:2025-03-24
  • 通讯作者: 高国华 E-mail:ghgao@chem.ecnu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号:22172053)

Porous poly(ionic liquid)s catalyzed carbon dioxide-promoted hydration of ethylene oxide

HONG Yang, LI Dandan, ZHANG Jingshun, ZHANG Ziwang, GAO Guohua   

  1. East China Normal University
  • Received:2024-12-30 Revised:2025-03-18 Online:2025-03-24 Published:2025-03-24
  • Contact: GAO Guohua E-mail:ghgao@chem.ecnu.edu.cn

摘要: 以刚性离子液体和有机碱为单体,通过自由基共聚法制备了一系列具有高比表面积和大孔结构的多孔聚离子液体。采用魔角旋转固体核磁、傅里叶变换红外光谱、扫描电子显微镜、氮气物理吸附脱附和热重分析对聚离子液体的结构、形貌和热稳定性进行了表征。多孔聚离子液体的比表面积为100.9-374.7 m2g-1,孔容为0.41-0.86 cm3g-1,活性位点均匀分布在孔隙结构内。多孔聚离子液体同时具有离子液体与有机碱活性中心,能够协同催化CO2辅助环氧乙烷水合反应,在低水合比(1.5:1)下,乙二醇收率达到96.5%,选择性为96.5%,达到了与均相催化剂相当的催化性能;CO2的助催化作用改变了水合反应的路径,极大地降低了反应的水合比,提高了乙二醇的选择性。此外,聚离子液体催化剂具有良好的底物适用性及可回收性,并且在烟气气氛下也具有良好的催化性能。

关键词: 乙二醇, 环氧乙烷, 多孔聚离子液体, CO2辅助水合反应

Abstract: As one of the energy-intensive processes, production of ethylene glycol with high selectivity from ethylene oxide under low hydration ratios is a challenge in the industry. In this study, a series of porous poly(ionic liquid)s with high specific surface area and macroporous structure were synthesized through free radical copolymerization of rigid ionic liquids and organic base monomers. The structure, microscopic morphology, and thermal stability of the poly(ionic liquid)s were characterized by magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), N2 physical adsorption-desorption, and thermogravimetric analysis (TGA). These poly(ionic liquid)s had a specific surface area ranging from 100.9 to 374.7 m2g?1, a pore volume ranging from 0.41 to 0.86 cm3g?1, with active sites uniformly distribute within the porous structure. Porous poly(ionic liquid)s possessing both the active centers of ionic liquids and organic bases could synergistically catalyze the CO2-promoted hydration of ethylene oxide. Under a low hydration ratio of 1.5:1, high yield (96.5 %) and selectivity (96.5 %) of ethylene glycol were achieved, which were comparable to the corresponding homogeneous catalysts. The CO2-promoted catalysis alters the pathway of hydration reaction, significantly reducing the hydration ratio and improving the selectivity of ethylene glycol. In addition, the catalyst had good substrate applicability and recyclability, and it also showed good catalytic performance under flue gas atmosphere.

Key words: Ethylene glycol, Ethylene oxide, Porous poly(ionic liquids), CO2-promoted hydration reaction

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