SCI和EI收录∣中国化工学会会刊

Chin.J.Chem.Eng. ›› 2015, Vol. 23 ›› Issue (7): 1147-1152.DOI: 10.1016/j.cjche.2014.11.033

• CATALYSIS, KINETICS AND REACTION ENGINEERING • Previous Articles     Next Articles

Efficient synthesis of 1,6-hexamethylene diurethane through coupling transesterification and methoxycarbonylation with methyl phenyl carbonate as intermediate

Yong Yang1,3, Jihai Tang1, Xian Chen1, Zhaoyang Fei1,2, Mifen Cui1, Xu Qiao1,2   

  1. 1 College of Chemistry and Chemical Engineering, Nanjing Tech University, Nanjing 210009, China;
    2 State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, China;
    3 College of Life Science and Chemical Engineering, Huaiyin Institute of Technology, Huaiyin 223003, China
  • Received:2014-06-26 Revised:2014-11-04 Online:2015-08-21 Published:2015-07-28
  • Contact: Xian Chen, Xu Qiao
  • Supported by:

    Supported by the National Natural Science Foundation of China (21276126, 21306089) and the Jiangsu Province Higher Education Natural Science Foundation (09KJA530004, 13KJB530006).

Efficient synthesis of 1,6-hexamethylene diurethane through coupling transesterification and methoxycarbonylation with methyl phenyl carbonate as intermediate

Yong Yang1,3, Jihai Tang1, Xian Chen1, Zhaoyang Fei1,2, Mifen Cui1, Xu Qiao1,2   

  1. 1 College of Chemistry and Chemical Engineering, Nanjing Tech University, Nanjing 210009, China;
    2 State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, China;
    3 College of Life Science and Chemical Engineering, Huaiyin Institute of Technology, Huaiyin 223003, China
  • 通讯作者: Xian Chen, Xu Qiao
  • 基金资助:

    Supported by the National Natural Science Foundation of China (21276126, 21306089) and the Jiangsu Province Higher Education Natural Science Foundation (09KJA530004, 13KJB530006).

Abstract: A reaction coupling system of transesterification and methoxycarbonylation with methyl phenyl carbonate (MPC) as intermediate was established to efficiently prepare 1,6-hexamethylene diurethane (HDU) from 1,6-hexamethylene diamine (HDA). The feasibility of the system was explored using the thermodynamics analysis, the reaction mechanism and the experiment results. The optimal reaction was carried out to get higher HDU yield. The thermodynamic analysis showed that the methoxycarbonylation of HDA with MPC, the Gibbs free energy of which was negative, was a spontaneous process. Furthermore, the equilibrium constant of the methoxycarbonylation of HDA with MPC was much greater than that of the transesterification of dimethyl carbonate (DMC) with phenol, so the reaction coupling could be realized under mild conditions. The reaction mechanismanalysis indicated that phenoxy anion was the key species for reaction coupling. HigherMPC concentration was detected when sodium phenoxide was used as transesterification reactant with DMC, since the phenoxy anion of sodium phenoxide could be dissociated more easily. Sodium phenoxide was more suitable to prepare HDU through reaction coupling. A yield of HDU as high as 98.3% could be reached under the optimal conditions of mPhONa/mDMC = 0.027 and nDMC/nHDA = 8/1 at 90 ℃ in 2 h.

Key words: Methyl phenyl carbonate, 1,6-Hexamethylene diurethane, Transesterification, Methoxyl carbonate, Reaction coupling

摘要: A reaction coupling system of transesterification and methoxycarbonylation with methyl phenyl carbonate (MPC) as intermediate was established to efficiently prepare 1,6-hexamethylene diurethane (HDU) from 1,6-hexamethylene diamine (HDA). The feasibility of the system was explored using the thermodynamics analysis, the reaction mechanism and the experiment results. The optimal reaction was carried out to get higher HDU yield. The thermodynamic analysis showed that the methoxycarbonylation of HDA with MPC, the Gibbs free energy of which was negative, was a spontaneous process. Furthermore, the equilibrium constant of the methoxycarbonylation of HDA with MPC was much greater than that of the transesterification of dimethyl carbonate (DMC) with phenol, so the reaction coupling could be realized under mild conditions. The reaction mechanismanalysis indicated that phenoxy anion was the key species for reaction coupling. HigherMPC concentration was detected when sodium phenoxide was used as transesterification reactant with DMC, since the phenoxy anion of sodium phenoxide could be dissociated more easily. Sodium phenoxide was more suitable to prepare HDU through reaction coupling. A yield of HDU as high as 98.3% could be reached under the optimal conditions of mPhONa/mDMC = 0.027 and nDMC/nHDA = 8/1 at 90 ℃ in 2 h.

关键词: Methyl phenyl carbonate, 1, 6-Hexamethylene diurethane, Transesterification, Methoxyl carbonate, Reaction coupling