咪唑基双磺酸官能化离子液体高效催化液相贝克曼重排:实验和 COSMO-RS 计算

IF 9.1 Q1 ENGINEERING, CHEMICAL Green Chemical Engineering Pub Date : 2023-01-12 DOI:10.1016/j.gce.2023.01.002
Xin Guo , Zhiyuan Wang , Ye Yang , Jiahui Zhang , Yanduo Liu , Zhiyuan Mu , Siqi Jiang , Chunxiao Ren , Dan Lv , Yufeng Hu , Zhichang Liu
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引用次数: 0

摘要

化工行业需要开发一种产量高且环保的ε-己内酰胺(CPL)生产技术。该技术对设计和合成用于环己酮肟(CHO)到 CPL 的液相贝克曼重排的高性能催化剂具有极大的需求。本研究成功合成了高效且收率优异的 3-甲基-1-(丙基-4-磺酰基)咪唑鎓甲磺酸盐([PHSO3MIM][MSA])。当 ZnCl2 与 [PHSO3MIM][MSA] 的最佳摩尔比为 0.02 时,该化合物在 90 °C 下 1 小时内对 CPL 具有高选择性(94%)。有趣的是,傅立叶变换红外光谱(FT-IR)研究表明,均匀分布的 ZnCl2 和 [PHSO3MIM][MSA] 形成了功能性布氏路易斯酸型离子液体(ILs)。此外,CHO 和 IL 之间还形成了氢键(H-bond)。经过十次反应循环后,回收的[PHSO3MIM][MSA]-ZnCl2 的结构没有发生明显变化。利用 COSMO-RS 模型预测了 ILs 的溶解度,结果表明[PHSO3MIM][MSA]是 CHO 在液相贝克曼重排中转化为 CPL 的理想候选物质。最后,IL 与 CHO 之间 H 键相互作用的理论模型得到了进一步证实,为反应机理的推进提供了支持。这为液相贝克曼重排反应中的 CPL 生产技术提供了一条可行的途径。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

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Highly efficient catalyzed by imidazolium-based dual-sulfonic acid functionalized ionic liquids for liquid phase Beckmann rearrangement: experiments and COSMO-RS calculations

A production technique with the high yield and environmentally friendly process need be developed for ε-Caprolactam (CPL) in the chemical industry. This technology is highly desired to design and synthesize high−performance catalysts for liquid phase Beckmann rearrangement of cyclohexanone oxime (CHO) to CPL. In this work, 3-methyl-1-(propyl-4-sulfonyl) imidazolium methanesulfonate ([PHSO3MIM][MSA]) with highly efficient and excellent yield is synthesized successfully. When the optimum molar ratio of ZnCl2 over [PHSO3MIM][MSA] was 0.02, it exhibits the high selectivity (94%) of CPL at 90 °C for 1 h. Interestingly, Fourier-transform infrared (FT-IR) investigations show that the functional Brønsted−Lewis acidic types of ionic liquids (ILs) are formed by the uniformly distributed ZnCl2 and [PHSO3MIM][MSA]. In addition, the hydrogen bond (H-bond) is formed between CHO and ILs. After ten reaction cycles, no significant structure changes are observed in the recovered [PHSO3MIM][MSA]·ZnCl2. The solubilities of ILs are predicted by using COSMO-RS model, the results show that [PHSO3MIM][MSA] is a promising candidate for the liquid phase Beckmann rearrangement of CHO into CPL. Finally, a theoretical model of the H-bond interactions between ILs and CHO is further confirmed to support the advance of reaction mechanism. A feasible way is provided for the CPL production technique in the liquid phase Beckmann rearrangement reaction.

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来源期刊
Green Chemical Engineering
Green Chemical Engineering Process Chemistry and Technology, Catalysis, Filtration and Separation
CiteScore
11.60
自引率
0.00%
发文量
58
审稿时长
51 days
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OFC: Outside Front Cover Outside Back Cover Outside Back Cover OFC: Outside Front Cover Integration of physical information and reaction mechanism data for surrogate prediction model and multi-objective optimization of glycolic acid production
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