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Efficient synthesis of dimethyl hexane-1,6-dicarbamate via methoxycarbonylation of 1, 6-hexanediamine with methyl carbamate over acid-base enhanced CeO2
Molecular Catalysis ( IF 3.9 ) Pub Date : 2023-08-21 , DOI: 10.1016/j.mcat.2023.113453
Junya Cao , Xiaoxuan Wang , Liguo Wang , Yan Cao , Xiang Hui , Peng He , Huiquan Li

The carbonylation of 1,6-hexanediamine (HDA) is an important method for the production of dimethyl hexane-1,6-dicarbamate (HDC), which is of great significance for the non-phosgene synthesis of hexamethylene-diisocyanate. This research focuses on the synthesis of HDC through the methoxycarbonylation of HDA using methyl carbamate as a carbonyl source. The study investigates the utilization of CeO2 catalyst prepared via H2O2single bondassisted precipitation. Various characterization techniques, including N2 physical adsorption and desorption, SEM, TEM, XRD, NH3single bondTPD, CO2single bondTPD, and XPS are employed to analyze the texture and structure of CeO2 catalysts prepared through different methods. In situ FTIR experiments are conducted to monitor the potential process of the carbonylation reaction. The results of the in situ FTIR spectroscopy clearly indicate the formation of polyurea as an intermediate compound, which subsequently converts into HDC. The findings demonstrate that CeO2 prepared using the hydrogen peroxide precipitation method exhibits a larger specific surface area, stronger acid-base properties, and a higher content of surface-adsorbed oxygen. These characteristics are favorable for the carbonylation reaction. Under optimized conditions, the HDC yield reaches 96.0% with complete conversion of HDA. The catalyst's activity essentially maintained throughout ten cycles. Additionally, a substrate versatility study reveals that CeO2 exhibits excellent catalytic properties for synthesizing a range of aliphatic and alicyclic dicarbamates.



中文翻译:

酸碱增强 CeO2 上 1, 6-己二胺与氨基甲酸甲酯甲氧基羰基化高效合成己烷-1,6-二氨基甲酸二甲酯

1,6-己二胺(HDA)的羰基化是生产1,6-己二氨基甲酸二甲酯(HDC)的重要方法,对于六亚甲基二异氰酸酯的非光气合成具有重要意义。本研究的重点是使用氨基甲酸甲酯作为羰基源,通过 HDA 的甲氧基羰基化合成 HDC。该研究探讨了通过H 2 O 2辅助沉淀制备的CeO 2催化剂的利用。采用N 2物理吸附和解吸、SEM、TEM、XRD、NH 3 TPD、CO 2 TPD 和XPS 等多种表征技术来分析CeO 2的织构和结构。单键单键单键通过不同方法制备的催化剂。进行原位FTIR 实验来监测羰基化反应的潜在过程。原位FTIR 光谱的结果清楚地表明聚脲作为中间化合物的形成,随后转化为 HDC。研究结果表明,CeO 2采用过氧化氢沉淀法制备的产物具有较大的比表面积、较强的酸碱性能和较高的表面吸附氧含量。这些特性有利于羰基化反应。在优化条件下,HDC收率达到96.0%,HDA完全转化。催化剂的活性在十个循环中基本保持。此外,底物多功能性研究表明,CeO 2在合成一系列脂肪族和脂环族二氨基甲酸酯方面表现出优异的催化性能。

更新日期:2023-08-21
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