碳酸二甲酯与苯酚酯交换合成碳酸二苯酯的热力学性质及均相催化剂(英文)  

The Thermodynamic Properties and Homogeneous Catalysts for the Synthesis of Diphenyl Carbonate by Transesterification of Dimethyl Carbonate with Phenol

作　　者：梅付名[1] 李光兴[1] 

机构地区：[1]华中科技大学化学系,湖北武汉430074

出　　处：《合成化学》2003年第4期320-326,共7页Chinese Journal of Synthetic Chemistry

摘　　要：在 2 98 .1 5 K,1 0 1 .32 5 k Pa条件下 ,液态碳酸二甲酯 ( DMC)的标准 Gibbs自由能和熵分别估算为 - 472 .3k J· mol- 1和 2 4 5 .2 J· mol- 1· K- 1。在 2 98K～ 5 2 3K计算了由 DMC和苯酚生成碳酸二苯酯 ( DPC)和苯甲醚反应的热力学性质 (Δr H0m,Δr S0m,Δr G0m 和平衡常数 )。计算出的热力学性质表明 ,DMC和苯酚酯交换合成 DPC反应是吸热的 ,并且在热力学上是不利的。研究了n- Bu2 Sn O,Ti( OC4 H9) 4,Al Cl3和 Zn Cl2 四种酯交换法合成 DPC反应的催化剂 ,其中 n-Bu2 Sn O具有最高的催化活性。热力学计算和实验结果均表明 ,合成 DPC反应的最佳温度为45 3K。当以 n- Bu2 Sn O为催化剂 ,n(苯酚 )∶ n( DMC) =4∶ 1时 ,DPC的产率和选择性分别为43.0 %和 88.7%。The Gibbs free energy of formation and entropy of liquid dimethyl carbonate(DMC) at 298.15K and 101.325kPa were estimated to be -472.3 kJ·mol -1 and 245.2 J·mol -1 ·K -1 respectively. The thermodynamic properties (Δ rH 0 m,Δ rS 0 m,Δ rG 0 m and equilibrium constant) of the reactions for the production of diphenyl carbonate(DPC) and anisole between DMC and phenol from 298K to 523K were calculated. These values indicated that the reaction of transesterification of DMC with phenol to DPC was endothermic and thermodynamically unfavorable. n Bu 2SnO, Ti(OC 4H 9) 4, AlCl 3 and ZnCl 2 were tested to catalyze the synthesis of DPC by transesterification of DMC with phenol. n Bu 2SnO had the highest catalytic activity among them. The optimum temperature was 453K for the synthesis of DPC. When the molar ratio of phenol to dimethyl carbonate was 4∶1, the yield and selectivity of DPC were 43.0% and 88.7% respectively using n Bu 2SnO as a catalyst.

关 键 词：碳酸二甲酯 碳酸二苯酯 酯交换法 热力学 苯酚 均相催化剂 

分 类 号：O625.523[理学—有机化学]