Zn(OAc)2·2H_2O催化草酸二苯酯脱羰基合成碳酸二苯酯反应的研究  

Study on the synthesis of diphenyl carbonate from decarbonylation of diphenyl oxalate over Zn(OAc)2·2H_2O

作　　者：王胜平[1] 马新宾[1] 巩金龙[1] 李振花[1] 许根慧[1] 

机构地区：[1]天津大学化工学院绿色合成与转化教育部重点实验室,天津300072

出　　处：《化学试剂》2004年第4期197-200,共4页Chemical Reagents

基　　金：国家自然科学基金(20276050);天津市科技攻关培育项目及高等学校骨干教师资助计划。

摘　　要：研究了Zn(OAc)2·2H2O催化草酸二苯酯(DPO)脱羰基合成碳酸二苯酯(DPC)反应,考察了反应温度、反应时间、DPO和催化剂用量物质的量配比对DPC选择性、DPC收率和DPO转化率的影响。确定的较佳反应条件是反应温度260℃,反应时间3h,DPO和催化剂用量物质的量配比是100∶15。运用MXXC、Benson等基团贡献法,对草酸二苯酯脱羰基反应的平衡常数进行了估算,得到ΔrH533=2707kJ/mol,KP=13×109。DPO脱羰基合成DPC反应体系中存在副反应。The synthesis of diphenyl carbonate (DPC) from decarbonylation of diphenyl oxalate (DPO) over Zn(OAc) 2·2H 2O was carried out.The equilibrium constant of decarbonylation of diphenyl oxalate was calculated by various group contributions.The hydrolysis reaction of DPO was the side reaction and the by products were phenol and oxalic acid,which decarboxylated or reacted with phenol to produce 2 hydroxy benzoic acid phenyl ester.The influence of reaction time,reaction temperature,and mol ratio of DPO to Zn(OAc) 2·2H 2O on selectivity of DPC,yield of DPC and conversion of DPO was studied.And the optimal conditions were reaction at 260℃,100∶1.5 mol ratio of DPO to Zn(OAc) 2· 2H 2O for 3h.

关 键 词：草酸二苯酯 碳酸二苯酯 脱羰基反应 热力学分析 副反应 催化反应 

分 类 号：O625.323[理学—有机化学]