Heterogeneous synthesis of dimethylhexane-1,6-dicarbamate from 1,6-hexanediamine and methyl carbonate in methanol over a CeO2 catalyst

doi:10.1016/j.cjche.2014.03.002

›› 2015, Vol. 23 ›› Issue (2): 446-450.DOI: 10.1016/j.cjche.2014.03.002

Heterogeneous synthesis of dimethylhexane-1,6-dicarbamate from 1,6-hexanediamine and methyl carbonate in methanol over a CeO₂ catalyst

Yan Cao, Huiquan Li, Xintao Li, Liguo Wang, Ganyu Zhu, Qing Tang

Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences(CAS), Beijing 100190, China

收稿日期:2013-11-01 修回日期:2014-03-12 出版日期:2015-02-28 发布日期:2015-03-01
通讯作者: Huiquan Li
基金资助:
Supported by the Science and Technology Ministry of China (2013BAC11B03) and National Nature Science Foundation of China (21476244, 21206180, 21406245).

Heterogeneous synthesis of dimethylhexane-1,6-dicarbamate from 1,6-hexanediamine and methyl carbonate in methanol over a CeO₂ catalyst

Yan Cao, Huiquan Li, Xintao Li, Liguo Wang, Ganyu Zhu, Qing Tang

Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences(CAS), Beijing 100190, China

Received:2013-11-01 Revised:2014-03-12 Online:2015-02-28 Published:2015-03-01
Supported by:
Supported by the Science and Technology Ministry of China (2013BAC11B03) and National Nature Science Foundation of China (21476244, 21206180, 21406245).

摘要/Abstract

摘要： The efficient synthesis of dimethylhexane-1,6-dicarbamate (HDC) from 1,6-hexanediamine (HDA) and methyl carbonate over a series of heterogeneous catalysts (e.g., MgO, Fe₂O₃, Mo₂O₃, and CeO₂) was investigated. The reaction pathway was confirmed as an alcoholysis reaction through a series of designed experiments. Under optimized conditions, 100% HDA conversion with 83.1% HDC_total and 16.9% polyurea was obtained using a onestep with high temperature procedurewith CeO₂ as the catalyst. A newtwo-stepwith variable temperature technology was developed based on the reaction pathway to reduce the polyurea yield. Using the proposed method, the HDC_total yield reached 95.2%, whereas the polyurea yield decreased to 4.8%. The CeO₂ catalyst showed high stability and did not exhibit any observable decrease in the HDC yield or any structural changes after four recycling periods.

关键词: Heterogeneous, Dimethylhexane-1,6-dicarbamate, Methyl carbonate, Reaction pathway, Two-step variable-temperature technology

Abstract: The efficient synthesis of dimethylhexane-1,6-dicarbamate (HDC) from 1,6-hexanediamine (HDA) and methyl carbonate over a series of heterogeneous catalysts (e.g., MgO, Fe₂O₃, Mo₂O₃, and CeO₂) was investigated. The reaction pathway was confirmed as an alcoholysis reaction through a series of designed experiments. Under optimized conditions, 100% HDA conversion with 83.1% HDC_total and 16.9% polyurea was obtained using a onestep with high temperature procedurewith CeO₂ as the catalyst. A newtwo-stepwith variable temperature technology was developed based on the reaction pathway to reduce the polyurea yield. Using the proposed method, the HDC_total yield reached 95.2%, whereas the polyurea yield decreased to 4.8%. The CeO₂ catalyst showed high stability and did not exhibit any observable decrease in the HDC yield or any structural changes after four recycling periods.

Key words: Heterogeneous, Dimethylhexane-1,6-dicarbamate, Methyl carbonate, Reaction pathway, Two-step variable-temperature technology

Yan Cao, Huiquan Li, Xintao Li, Liguo Wang, Ganyu Zhu, Qing Tang. Heterogeneous synthesis of dimethylhexane-1,6-dicarbamate from 1,6-hexanediamine and methyl carbonate in methanol over a CeO₂ catalyst[J]. , 2015, 23(2): 446-450.

参考文献

[1] R.G. Deleon, A. Kobayashi, T. Yamauchi, J. Ooishi, T. Baba, M. Sasaki, F. Hiarata, Catalytic methoxycarbonylation of 1,6-hexanediamine with dimethyl carbonate to dimethylhexane-1,6-dicarbamate using Bi(NO₃)₃, Appl. Catal. A Gen. 225 (2002) 43-49.
[2] H. Zhou, F. Shi, X. Tian, Q. Zhang, Y. Deng, Synthesis of carbamates from aliphatic amines and dimethyl carbonate catalyzed by acid functional ionic liquids, J. Mol. Catal. A Chem. 271 (2007) 89-92.
[3] T. Baba,M. Fujiwara, A.Oosaku,A.Kobayashi,R.G.Deleon, Y. Ono, Catalytic synthesis of N-alkyl carbamates by methoxycarbonylation of alkylamines with dimethyl carbonate suing Pb(NO₃)2, Appl. Catal. A Gen. 227 (2002) 1-6.
[4] F. Li, J. Miao, Y.Wang, X. Zhao, Synthesis of methyl N-phenyl carbamate from aniline and dimethyl carbonate over supported zirconia catalyst, Ind. Eng. Chem. Res. 45 (2006) 4892-4897.
[5] J. Zhang, C.G. Xia, Study on selectivity of reductive carbonylation of nitrobenzene to carbamates, Acta.Chim. Sin. 61 (2003) 427-429.
[6] P.P. Xu, F.X. Zhang, Oxidative carbonylation of aniline by Pd/C catalyst, Chin. J. Appl. Chem. 14 (1997) 41-45.
[7] M.K. Zhang, J.R. Deng, H.J. Deng, M.L. Fan, D.L. Sun, Study on synthesis of 1,6- hexamethylene diurethane using urea as carbonylation regent, Chem. Ind. Eng. Prog. 24 (2005) 1151-1154.
[8] T. Masuda, D. Saylik, L. Diebele, Production of Aliphatic Isocyanate: JP6239826, 1994. 10-16.
[9] B. Han, W. Zhao, X. Qin, Y. Li, Y. Sun, W. Wei, Synthesis of dimethylhexane-1,6- dicarbamate from 1,6-hexamethylenediamine and methyl carbamate using lead dioxide as catalyst, Catal. Commun. 33 (2013) 38-41.
[10] D.L. Sun, J.R. Deng, Chao Z.S. , Catalysis over zinc-incorporated berlinite (ZnAlPO4) of the methoxycarbonylation of 1,6-hexanediamine with dimethyl carbonate to form dimethylhexane-1,6-dicarbamate, Chem. Cent. J. (2007) 1-27, http://dx.doi.org/10. 1186/1752-153X-1-27 (1).
[11] D.L. Sun, S.J. Xie, J.R. Deng, C.J. Huang, E. Ruckenstein, Z.S. Chao, CH3COONa as an effective catalyst for methoxycarbonylation of 1,6-hexanediamine by dimethyl carbonate to dimethylhexane-1,6-dicarbamate, Green Chem. 12 (2010) 483-490.
[12] D. Monica, Q. Eugenio, F. Epifano, Highly selective carbamation of aliphatic diamines undermild conditions using Sc(OTf)3 as catalyst and dimethyl carbonate as a phosgene substitute, Appl. Catal.B. 66 (2006) 72-80.
[13] H. Zhang, X. Guo, Q. Zhang, Y. Ma, H. Zhou, J. Li, L. Wang, Y. Deng, Synthesis of dialkylhexamethylenediacarbamate from 1,6-hexamethylenediamine and alkyl carbamate over Y(NO₃)₃·6H₂O catalyst, J. Mol. Catal. A Chem. 296 (2008) 36-41.
[14] X. Guo, J. Shang, X. Ma, J. Li, H. Zhang, X. Cui, F. Shi, Y. Deng, Synthesis of dialkyl hexamethylene-1,6-dicarbamate from 1,6-hexamethylenediamine and alkyl carbamate over FeCl3 as catalyst, Catal. Commun. 10 (2009) 1248-1251.
[15] J. Shang, X. Guo, F. Shi, Y. Ma, F. Zhou, Y. Deng, N-substituted carbamates syntheses with alkyl carbamates as carbonyl source over Ni-promoted Fe3O4 catalyst, J. Catal. 279 (2011) 328-336.

Heterogeneous synthesis of dimethylhexane-1,6-dicarbamate from 1,6-hexanediamine and methyl carbonate in methanol over a CeO₂ catalyst

Heterogeneous synthesis of dimethylhexane-1,6-dicarbamate from 1,6-hexanediamine and methyl carbonate in methanol over a CeO₂ catalyst

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