化学负载型离子液体催化制备环状碳酸酯的研究
文献类型：学位论文
| 作者 | 陈曦 |
| 学位类别 | 硕士 |
| 答辩日期 | 2012-05-25 |
| 授予单位 | 中国科学院研究生院 |
| 导师 | 张锁江 ; 成卫国 |
| 关键词 | 化学负载 离子液体 CO2 环状碳酸酯 环加成反应 |
| 其他题名 | Synthesis of Cyclic Carbonates Catalyzed by Chemically Immobilized Ionic Liquids |
| 学位专业 | 化学工程 |
| 中文摘要 | 环状碳酸酯的合成是一个能够有效化学固定CO2这一C1资源的有机反应，近年来受到了越来越多的关注。而作为新兴的绿色介质，离子液体具有结构可设计、稳定性高的优良性质，可以通过化学键方式实现负载化，形成非均相催化剂，达到简化分离的效果，这使其在这一环加成反应的催化方面应用前景广阔。针对CO2和环氧化合物反应制备环状碳酸酯的过程中通常出现的催化剂活性低、不易分离、反应条件苛刻、需要添加助溶剂或助催化剂等关键性问题，本论文开展了化学负载型离子液体催化合成环状碳酸酯的研究。论文主要创新性工作及成果如下： 1. 设计了用于制备环状碳酸酯的树脂负载多羟基季铵类离子液体催化剂，该类催化剂稳定性好，催化活性高，选择性好。实验结果表明，以树脂负载二羟乙基乙基铵溴盐(PS-DHEEAB)为催化剂，在不添加任何助溶剂或助催化剂的温和反应条件下(催化剂用量2.0 mol%，110 ℃，2.0 MPa，4 h)可实现99.0%的环氧丙烷转化率和99.0%以上的碳酸丙烯酯选择性，而且催化剂在循环使用6次后其活性未见明显降低；并且该催化体系同样适用于其他端位环氧化合物以及氮杂环化合物。 2. 设计合成了多功能的介孔分子筛SBA-15负载的1,2,4-三氮唑类离子液体，载体与活性组分中均含有协同催化的基团，可同时活化环氧化合物和CO2。研究进一步验证了羟基的协同催化作用，基于载体与活性组分中的羟基等基团的协同催化作用，SBA-15负载的功能化1,2,4-三氮唑类离子液体催化剂具有良好的反应活性，在最佳反应条件下都能高效、稳定地催化环加成反应；该催化剂同样表现出了良好的热稳定性和催化稳定性，并且适用于各类环氧化合物。 3. 研究了离子液体阳离子中羟基的强化氢键效应，发现羟基数目对催化活性有显著影响，提出了多羟基的强化氢键诱导环氧化合物开环的反应机理。 |
| 英文摘要 | The synthesis of cyclic carbonates can fix CO2 as a C1 resource, which has received increasing attention in recent years. As novel green media, ionic liquids (ILs) have shown broad prospects in the catalysis of this cycloaddition reaction due to their thermal stability and widely tunable properties. So the ILs can also be chemically immobilized onto solid supports. This kind of supported catalyst can easily be separated from reaction system. In order to overcome disadvantages, such as unsatisfactory activities, difficulties in separation, tough reaction conditions and requirement of co-solvents or co-catalysts, the synthesis of cyclic carbonates using various immobilized IL catalysts has been systematically investigated. The major work and innovative results for this dissertation are as follows. 1. A series of polystyrene resin supported multi-hydroxyl functionalized ammonium based ILs was developed and showed high activity and selectivity for the coupling reaction of CO2 and epoxide under the mild conditions. It was found that a 99.0% conversion of propylene oxide with more than 99.0% propylene carbonate selectivity could be achieved by using polystyrene supported diethanolamineethyl bromide (PS-DHEEAB) as catalyst at catalyst amount 2.0 mol%, 110 ℃, 2.0 MPa and 4 h without any co-solvents or co-catalysts.. The catalyst showed little decrease in activity after 6 times recycling and also found to be extended to a variety of terminal epoxides and aziridines. 2. A series of SBA-15 supported 1,2,4-triazolium based ILs was developed as multi-function catalysts. Functional groups both in the supports and the active components can play a role of synergetic catalysis, which has been confirmed by experiment and characterization. And it may also have an effect of the activation of CO2. Among these catalyst, the SBA-15 supported 1,2,4-triazolium based IL catalysts exhibit good performance under milder conditions. The catalysts also showed good reusability and was found to be efficient to other epoxides. 3. The effect of the catalysts with different number of hydroxyl group in the cation of the IL on the reaction was systematically investigated. The mechanism of the hydrogen bonding strength of the -OH functional groups was proposed. |
| 语种 | 中文 |
| 公开日期 | 2013-09-25 |
| 源URL | [http://ir.ipe.ac.cn/handle/122111/1824]  |
| 专题 | 过程工程研究所_研究所（批量导入） |
| 推荐引用方式 GB/T 7714 | 陈曦. 化学负载型离子液体催化制备环状碳酸酯的研究[D]. 中国科学院研究生院. 2012. |
入库方式： OAI收割
来源：过程工程研究所
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。