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过程工程学报 ›› 2022, Vol. 22 ›› Issue (3): 393-402.DOI: 10.12034/j.issn.1009-606X.220438CSTR: 32067.14.jproeng.220438

• 研究论文 • 上一篇    下一篇

己二胺与碳酸二乙酯催化羰化合成己二氨基甲酸酯

袁浠焘1， 黄科林2,3*， 王利国4,6， 贺鹏4*， 曹妍4， 徐爽4， 陈家强4， 李会泉4,5
  

  1. 1. 广西民族大学化学化工学院，广西 南宁 530008 2. 中国科技开发院广西分院，广西 南宁 530022 3. 广西产研院新型功能材料研究所有限公司，广西 南宁 530022 4. 中国科学院过程工程研究所绿色过程与工程重点实验室，湿法冶金清洁生产技术国家工程实验室，北京 100190 5. 中国科学院大学化工学院，北京 100049 6. 大连洁净能源创新研究院，辽宁 大连 116023
  • 收稿日期:2020-12-31 修回日期:2021-04-08 出版日期:2022-03-28 发布日期:2022-03-28
  • 通讯作者: 贺鹏 phe@ipe.ac.cn
  • 作者简介:袁浠焘(1995-)，男，江西省九江市人，硕士研究生，生物化工专业，E-mail: 2635251804@qq.com；通讯联系人，黄科林，E-mail: huanghn@sina.com；贺鹏，E-mail: phe@ipe.ac.cn.
  • 基金资助:
    STS中科院区域重点项目;中国科学院洁净能源先导科技专项

Catalytic carbonylation of hexanediamine with diethyl carbonate to synthesis hexamethylene dicarbamate

Xitao YUAN1,  Kelin HUANG2,3*,  Liguo WANG4,6,  Peng HE4*,  Yan CAO4,  Shuang XU4, Jiaqiang CHEN4,  Huiquan LI4,5   

  1. 1. College of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning, Guangxi 530008, China 2. China Academy of Science and Technology Development Guangxi Branch, Nanning, Guangxi 530022, China 3. Guangxi Industry Research Institute New Functional Materials Research Institute Co., Ltd., Nanning, Guangxi 530022, China 4. CAS Key laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China 5. School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China 6. Dalian National Laboratory for Clean Energy, Dalian, Liaoning 116023, China
  • Received:2020-12-31 Revised:2021-04-08 Online:2022-03-28 Published:2022-03-28
  • Contact: Peng He phe@ipe.ac.cn

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摘要： 以碳酸二乙酯(DEC)、1,6-己二胺(HDA)为原料、无水醋酸锰为催化剂，合成了1,6-六亚甲基二氨基甲酸乙酯(HDEC)。通过红外光谱、核磁共振氢谱、气相色谱确定HDEC标样的结构和纯度，并建立了定量分析方法。进一步采用气质联用对反应的主副产物进行定性分析，推测反应路径。同时，对合成工艺进行反应参数优化，并推测反应机理。结果表明，该反应通过两步实现，首先HDA与DEC反应生成单取代的1-(6-氨基)-六亚甲基单氨基甲酸乙酯(HMEC)中间体，HMEC进一步与DEC羰化反应生成HDEC目标产物，同时反应过程中DEC与HDA以及HMEC反应生成脲类副产物。在最佳反应条件原料DEC与HDA摩尔比为3.5:1、反应温度120℃、无水醋酸锰催化剂用量为HAD初始用量的15%、反应时间5 h、转速400 r/min下，HDA转化率为100%，HDEC收率达89.6%。本研究为非光气法合成六亚甲基二异氰酸酯(HDI)重要中间体HDEC提供理论借鉴。

关键词: 碳酸二乙酯, 1,6-己二胺, 1,6-六亚甲基二氨基甲酸乙酯, 六亚甲基二异氰酸酯, 醋酸锰, 非光气

Abstract: Hexamethylene dicarbamate (HDI) is an important aliphatic isocyanate are often used in aerospace, aviation, and polymer materials. Compared with aromatic isocyanates, HDI does not contain a benzene ring and has a symmetrical carbon chain skeleton, which makes it light stable and highly decorated. Studies have shown that the non-phosgene method can be used to prepare HDI through the thermal decomposition of the key intermediate hexamethylene dicarbamate. In this work, 1,6-hexanediamine (HDA) and diethyl carbonate (DEC) are used to synthesis hexamethylene dicarbamate ethyl ester (HDEC) under the catalysis of manganese acetate anhydrous. The structure and purity of the self-made HDEC standard sample are determined by FT-IR, 1H-NMR and TG, and a quantitative analysis method is established. Furthermore, qualitative analysis of the main and side products of the reaction is carried out by GC-MS, and the reaction pathway is inferred. At the same time, the reaction parameters are optimized and the reaction mechanism is speculated. The results show that the reaction is achieved in two steps. First, HDA reacts with DEC to form a monosubstituted 1-(6-amino)-hexamethylene monocarbamate (HMEC) intermediate, the process is that manganese acetate attacks -NH2 at one end of HDA to form reactive intermediate I [H2N(CH2)6NHCOCH3], and reactive intermediate I reacts with DEC to form HMEC. Second, HMEC further reacts with DEC to form HDEC target product, the process is that manganese acetate attacks -NH2 at the end of HMEC to form reactive intermediate II [CH3CH2COONH(CH2)6NHCOCH3], and reactive intermediate (II) reacts with DEC to form HDEC. The CH3COOCH2CH3 reacts with Mn(OH)2 to form manganese acetate catalyst in the reaction process. In addition, DEC reacts with HDA and HMEC to form urea by-products during the reaction. Under the optimum reaction conditions, the molar ratio of DEC to HDA is 3.5:1, the reaction temperature is 120℃, the amount of anhydrous manganese acetate catalyst is 15% of HAD initial amount, the reaction time is 5 h and the rotating speed is 400 r/min, the conversion of HDA is 100% and the yield of HDEC is 89.6%.

Key words: Diethyl carbonate, 1,6-hexamethylene diamine, 1,6-hexamethylene dicarbamate, hexamethylene diisocyanate, manganese acetate, non-phosgene