| 离子聚合物不同间隔单元对催化CO2环加成反应的影响 | |
| Effect of Different Spacers in Ionic Polymers on Catalytic CO2 Cycloaddition Reaction | |
| 摘要: 在常压低温的温和条件下实现CO2与环氧化物环加成反应的高效催化转化仍是一个具有挑战的课题。以N-(三甲基硅基)咪唑和具有不同官能基团的二卤化物为前体，通过亲核取代反应形成重复的C—N键，简单高效地构建了一类新型的离子聚合物IP1~IP3，并采用FT-IR、扫描电镜、能量色散X射线谱面扫、比表面积与孔隙率分析和X射线光电子能谱对其进行了全面表征。离子聚合物IP1~IP3在pCO2=101 kPa时均能催化CO2与环氧化合物环加成形成环状碳酸酯，但不同官能基团的二卤化物形成具有不同间隔单元的离子聚合物催化性能存在差异，其中以酚羟基作为间隔单元的IP3具有最好的催化性能。在无溶剂、80℃、12 h和pCO2=101 kPa的反应条件下，IP3几乎定量地将环氧氯丙烷转化为对应的环状碳酸酯，并且具有良好的底物普适性。催化剂循环测试表明，IP3在重复使用10次后，产物的产率仍保持在92%以上，体现出优异的稳定性。 | |
| 关键词: 离子聚合物 二氧化碳 氢键供体 环状碳酸酯 催化 | |
| 基金项目: 浙江省自然科学基金(No.LY18B010007)资助。 | |
| Abstract: It is still a big challenge to efficiently catalyze cycloaddition of CO2 and epoxide under the mild condition of atmospheric pressure and low temperature. Herein, a family of novel ionic polymers IP1-IP3 has been facilely synthesized via nucleophilic substitution reaction between the precursors of N-trimethylsilyl imidazole and dihalides with different functional groups to form repeating C-N bonds. IP1-IP3 have been fully characterized by FT-IR, scanning electron microscope, X-ray energy dispersive spectrum mapping, specific surface area and porosity analyses, and X-ray photoelectron spectroscopy. The ionic polymers IP1-IP3 efficiently catalyzed the cycloaddition of CO2 and epoxides to afford cyclic carbonates at pCO2=101 kPa, but their catalytic activities varied with the spacers with different functional groups. Among the three ionic polymers, IP3 with a phenolic hydroxyl as the spacer showed the best catalytic performance. Under the optimized conditions of solvent-free, 80℃, 12 h, and pCO2=101 kPa, IP3 could quantitatively convert epichlorohydrin into its corresponding cyclic carbonate and showed broad substrate scope. Furthermore, IP3 could be recycled and reused 10 times without an obvious decrease in catalytic activity (Yield>92%), which indicates excellent stability. | |
| Keywords: ionic polymers carbon dioxide hydrogen bond donors cyclic carbonates catalysis | |
| 投稿时间：2022-01-13 修订日期：2022-04-15 | |
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| 朱立华,肖志音,钟伟,何亚兵.离子聚合物不同间隔单元对催化CO2环加成反应的影响[J].无机化学学报,2022,38(7):1299-1308. | |
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