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过程工程学报 ›› 2021, Vol. 21 ›› Issue (5): 587-593.DOI: 10.12034/j.issn.1009-606X.220087

• 过程与工艺 • 上一篇    下一篇

尿素羰化法绿色合成间苯二亚甲基二氨基甲酸酯

黄小雨1,2， 曹俊雅1， 韩风刚1,2， 王利国2,4*， 曹 妍2， 贺 鹏2，徐 爽2， 陈家强2， 仪 凡1,2， 李会泉2,3   

  1. 1. 中国矿业大学(北京)化学与环境工程学院，北京 100083 2. 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 3. 中国科学院大学化工学院，北京 100049 4. 中国科学院洁净能源创新研究院，辽宁 大连 116023
  • 收稿日期:2020-03-14 修回日期:2020-06-16 出版日期:2021-05-22 发布日期:2021-06-01
  • 通讯作者: Liguo Wang lgwang@ipe.ac.cn
  • 基金资助:
    国家自然科学基金资助项目;中国科学院洁净能源先导科技专项

Green synthesis of m-xylylene dicarbamate using urea as carbonylation reagent

Xiaoyu HUANG1,2,  Junya CAO1,  Fenggang HAN1,2,  Liguo WANG2,4*,  Yan CAO2,  Peng HE2,  Shuang XU2,  Jiaqiang CHEN2,  Fan YI1,2,  Huiquan LI2,3   

  1. 1. School of Chemical and Environmental Engineering, China University of Mining and Technology (Beijing), Beijing 100083, China 2. 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 3. School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China 4. Dalian National Laboratory for Clean Energy, Dalian, Liaoning 116023, China
  • Received:2020-03-14 Revised:2020-06-16 Online:2021-05-22 Published:2021-06-01
  • Contact: Liguo Wang lgwang@ipe.ac.cn

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摘要： 间苯二亚甲基二氨基甲酸酯(XDC)是非光气绿色合成特种异氰酸酯间苯二亚甲基二异氰酸酯(XDI)的关键中间体。本工作以TiO2作为催化剂，以尿素、间苯二甲胺(XDA)和乙醇为原料绿色高效合成XDC。通过气质联用，分析了XDC合成的主副反应，推测了主反应路径，并优化了反应工艺条件。结果表明，以TiO2作为催化剂时，催化剂用量为0.2 g，即约为15wt% XDA，乙醇用量为0.2 mol，n(urea):n(XDA)=3:1，反应温度为205℃，反应时间为6 h时，XDA转化率为100%，XDC收率可达82.4%。本研究提供了XDC绿色高效的合成方法。

关键词: 间苯二亚甲基二氨基甲酸酯, 间苯二亚甲基二异氰酸酯, 尿素, TiO2, 非光气

Abstract: M-xylylene diisocyanate (XDI) is an important special isocyanate that draws more and more attention in recent years. The introduction of the –CH2– group between the benzene ring and isocyanate group, which makes it resistant to yellowing, can be applied in the fields of high value-added polyurethanes, such as high-grade coatings, medical polyurethane, high-grade optical polyurethane, and so on. M-xylylene dicarbamate (XDC) is the key intermediate for the synthesis of XDI via the non-phosgene thermal decomposition route. In this work, a novel methodology for the synthesis of XDC via carbonylation of m-xylylenediamine (XDA) using urea as carbonylation reagent over TiO2 catalyst was proposed. The standard XDC sample was first synthesized by the reverse reaction between XDI and ethanol, and then, the qualitative analysis of the standard XDC sample was characterized by FT-IR and 1H-NMR to confirm its structure. The standard curve of XDC was then successfully established in liquid chromatography with a correlation coefficient of more than 0.999. The qualitative analysis of the target product was carried out by GC-MS, and the reaction path was primarily speculated. Furthermore, the effects of different catalysts, reaction temperature, reaction time, the molar ratio of raw materials, and catalyst dosage on the yield of XDC were studied. The results showed that using TiO2 as the catalyst, under the optimized conditions, the reaction temperature of 205℃, the reaction time of 6 h, n(urea):n(XDA) of 3:1, the amount of catalyst was 15wt% XDA, the conversion of XDA was 100%, and the yield of XDC could reach to as high as 82.4%. Therefore, this process not only provides a feasible route for green, effective, and economic production of XDC, but also provides a theoretical basis for the non-phosgene synthesis of special isocyanate XDI.

Key words: m-xylylene dicarbamate, m-xylylene diisocyanate, urea, TiO2, non-phosgene