以碳酸二甲酯和碳酸二苯酯为原料合成甲基苯基碳酸酯,对合成工艺条件进行了优化。结果表明,最佳合成条件为:n(碳酸二苯酯):n(碳酸二甲酯)=3∶1,反应温度170℃,滴加速度1.2 m L/min,催化剂用量为碳酸二苯酯质量的5.5%,反应时间2 h。在此...以碳酸二甲酯和碳酸二苯酯为原料合成甲基苯基碳酸酯,对合成工艺条件进行了优化。结果表明,最佳合成条件为:n(碳酸二苯酯):n(碳酸二甲酯)=3∶1,反应温度170℃,滴加速度1.2 m L/min,催化剂用量为碳酸二苯酯质量的5.5%,反应时间2 h。在此条件下,碳酸二苯酯转化率98.4%,甲基苯基碳酸酯收率69.8%。展开更多
A reaction coupling system of transesteri fication and methoxycarbonylation with methyl phenyl carbonate(MPC) as intermediate was established to ef ficiently prepare 1,6-hexamethylene diurethane(HDU) from 1,6-hexameth...A reaction coupling system of transesteri fication and methoxycarbonylation with methyl phenyl carbonate(MPC) as intermediate was established to ef ficiently 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 transesteri fication of dimethyl carbonate(DMC) with phenol, so the reaction coupling could be realized under mild conditions. The reaction mechanism analysis indicated that phenoxy anion was the key species for reaction coupling. Higher MPC concentration was detected when sodium phenoxide was used as transesteri fication 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 m Ph ONa/m DMC= 0.027 and n DMC/n HDA= 8/1 at 90 °C in 2 h.展开更多
文摘以碳酸二甲酯和碳酸二苯酯为原料合成甲基苯基碳酸酯,对合成工艺条件进行了优化。结果表明,最佳合成条件为:n(碳酸二苯酯):n(碳酸二甲酯)=3∶1,反应温度170℃,滴加速度1.2 m L/min,催化剂用量为碳酸二苯酯质量的5.5%,反应时间2 h。在此条件下,碳酸二苯酯转化率98.4%,甲基苯基碳酸酯收率69.8%。
基金Supported by the National Natural Science Foundation of China(21276126,21306089)the Jiangsu Province Higher Education Natural Science Foundation(09KJA530004,13KJB530006)
文摘A reaction coupling system of transesteri fication and methoxycarbonylation with methyl phenyl carbonate(MPC) as intermediate was established to ef ficiently 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 transesteri fication of dimethyl carbonate(DMC) with phenol, so the reaction coupling could be realized under mild conditions. The reaction mechanism analysis indicated that phenoxy anion was the key species for reaction coupling. Higher MPC concentration was detected when sodium phenoxide was used as transesteri fication 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 m Ph ONa/m DMC= 0.027 and n DMC/n HDA= 8/1 at 90 °C in 2 h.
