SCI和EI收录∣中国化工学会会刊

Chinese Journal of Chemical Engineering ›› 2023, Vol. 53 ›› Issue (1): 310-316.DOI: 10.1016/j.cjche.2021.12.026

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Synthesis and kinetics of 2,5-dicyanofuran in the presence of hydroxylamine ionic liquid salts

Xuan Gao1, Zhihui Li1,2, Dongsheng Zhang1, Xinqiang Zhao1, Yanji Wang1   

  1. 1. Hebei Provincial Key Lab of Green Chemical Technology and High Efficient Energy Saving, Hebei University of Technology, Tianjin 300130, China;
    2. School of Energy and Environmental Engineering, Hebei University of Technology, Tianjin 300130, China
  • Received:2021-07-26 Revised:2021-11-17 Online:2023-04-08 Published:2023-01-28
  • Contact: Zhihui Li,E-mail:lizhihui425@hebut.edu.cn;Yanji Wang,E-mail:yjwang@hebut.edu.cn
  • Supported by:
    This work was conducted with financial support from the National Natural Science Foundation of China (Nos. U20A20152, 21236001 and 21878069).

Synthesis and kinetics of 2,5-dicyanofuran in the presence of hydroxylamine ionic liquid salts

Xuan Gao1, Zhihui Li1,2, Dongsheng Zhang1, Xinqiang Zhao1, Yanji Wang1   

  1. 1. Hebei Provincial Key Lab of Green Chemical Technology and High Efficient Energy Saving, Hebei University of Technology, Tianjin 300130, China;
    2. School of Energy and Environmental Engineering, Hebei University of Technology, Tianjin 300130, China
  • 通讯作者: Zhihui Li,E-mail:lizhihui425@hebut.edu.cn;Yanji Wang,E-mail:yjwang@hebut.edu.cn
  • 基金资助:
    This work was conducted with financial support from the National Natural Science Foundation of China (Nos. U20A20152, 21236001 and 21878069).

Abstract: 2,5-Dicyanofuran (DCF) is an important biomass-derived platform compound primarily used to prepare bio-based adiponitrile, which is the key precursor for the synthesis of nylon 66 and 1,6-hexanediisocyanate (HDI). In this study, one-pot, green and safe synthesis of DCF from 2,5-diformylfuran (DFF) and hydroxylamine ionic liquid salts was proposed. Eco-friendly hydroxylamine ionic liquid salts were used as the nitrogen source. Ionic liquid exhibited three-fold function of cosolvent, catalysis and phase separation. The conversion of DFF and yield of DCF reached 100% under the following optimum reaction conditions: temperature of 120 ℃ for 70 min, volume ratio of paraxylene: [HSO3-b-Py]·HSO4 of 2:1, and molar ratio of DFF:(NH2OH)2·[HSO3-b-Py]·HSO4 of 1:1.5. The reaction mechanism for the synthesis of DCF was proposed, and the kinetic model was established. The reaction order with respect to DFF and intermediate product 2,5-diformylfuran dioxime (DFFD) was 1.06 and 0.16, and the reaction activation energy was 64.07 kJ·mol-1 and 59.37 kJ·mol-1 respectively. After the reaction, the ionic liquid was easy to separate, recover and recycle.

Key words: 2,5-Dicyanofuran, Hydroxylamine ionic liquid salts, Green synthesis, Kinetics

摘要: 2,5-Dicyanofuran (DCF) is an important biomass-derived platform compound primarily used to prepare bio-based adiponitrile, which is the key precursor for the synthesis of nylon 66 and 1,6-hexanediisocyanate (HDI). In this study, one-pot, green and safe synthesis of DCF from 2,5-diformylfuran (DFF) and hydroxylamine ionic liquid salts was proposed. Eco-friendly hydroxylamine ionic liquid salts were used as the nitrogen source. Ionic liquid exhibited three-fold function of cosolvent, catalysis and phase separation. The conversion of DFF and yield of DCF reached 100% under the following optimum reaction conditions: temperature of 120 ℃ for 70 min, volume ratio of paraxylene: [HSO3-b-Py]·HSO4 of 2:1, and molar ratio of DFF:(NH2OH)2·[HSO3-b-Py]·HSO4 of 1:1.5. The reaction mechanism for the synthesis of DCF was proposed, and the kinetic model was established. The reaction order with respect to DFF and intermediate product 2,5-diformylfuran dioxime (DFFD) was 1.06 and 0.16, and the reaction activation energy was 64.07 kJ·mol-1 and 59.37 kJ·mol-1 respectively. After the reaction, the ionic liquid was easy to separate, recover and recycle.

关键词: 2,5-Dicyanofuran, Hydroxylamine ionic liquid salts, Green synthesis, Kinetics