摘要
研究了ZnCl2催化剂催化草酸二苯酯脱羰基合成碳酸二苯酯反应,考察了反应温度、反应时间、草酸二苯酯和催化剂摩尔配比对碳酸二苯酯选择性、碳酸二苯酯收率和草酸二苯酯转化率的影响,确定了最佳的反应条件是反应温度280℃,反应时间3h,草酸二苯酯和催化剂摩尔配比是100∶0 5。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KP=1 3×109。确定了草酸二苯酯脱羰基反应的副反应,发现水在草酸二苯酯脱羰基合成碳酸二苯酯体系的副反应中起到了关键性作用。草酸二苯酯在酸催化剂作用下易发生水解反应,水的存在有利于副产物苯酚和水杨酸苯酯的生成。因此,限制反应体系中水的含量有助于碳酸二苯酯的生成。
Diphenyl carbonate (DPC) was synthesized by decarbonylation of diphenyl oxalate (DPO) over ZnCl2 catalyst DPC was analyzed by combined means of programmed temperature capillary gas chromatography and mass spectrometry The influence of various operating parameters on the process such as reaction temperature, reaction time and the molar ratio of DPO to ZnCl2 catalyst were investigated The optimal conditions were, at atmosphere pressure, reaction temperature 280℃, reaction time 3h, and n (DPO)∶n (ZnCl2) = 100∶05 The equilibrium constant of decarbonylation of diphenyl oxalate was calculated by various group contributions And the side reaction of decarbonylation of diphenyl oxalate was established It was found that water played a crucial role for side reaction in decarbonylation system Over acid catalysts, diphenyl oxalate was easy to be hydrolyzed Consequently, more byproducts, 2hydroxy benzoic acid phenyl ester and phenol, were generated Therefore, restricting water content conduced to produce diphenyl carbonate
出处
《天然气化工—C1化学与化工》
CAS
CSCD
北大核心
2003年第5期10-12,19,共4页
Natural Gas Chemical Industry
基金
国家自然科学基金(2 0 2 760 50 )
天津市科技攻关培育项目资助
