化学转化二氧化碳合成碳酸二苯酯的催化体系及反应机理研究  

Catalytic system and reaction mechanism for the conversion of carbon dioxide to diphenyl carbonate

作　　者：段振晓[1] 方涛[1] 廖崇静[1] 范国枝[1] 

机构地区：[1]武汉轻工大学化学与环境工程学院,武汉430023

出　　处：《环境化学》2013年第10期1841-1845,共5页Environmental Chemistry

基　　金：湖北省自然科学基金资助项目(2012DBA02001;2011CDC114);武汉市科技局重点科技攻关项目(20122082275)资助

摘　　要：研究了助催化剂存在下,ZnCl2催化CO2、苯酚和CCl4合成碳酸二苯酯(DPC),考察了助催化剂种类及催化剂用量的影响.结果表明,Bu4NBr、Cs2CO3和K2CO3不能有效促进ZnCl2的催化活性,而CF3SO3H则是一种有效的助催化剂.在ZnCl2用量相同的情况下,体系中加入CF3SO3H后,DPC产率由2.2%显著增加至17%.采用气相色质联用(GC-MS)对该催化体系的反应产物进行了定性分析,除生成主产物DPC外,还有氯甲酸苯酯、水杨酸苯酯(PS)和双(2-羟苯基)甲酮等副产物生成,在此基础上提出了DPC及副产物的可能生成机理.Diphenyl carbonate （DPC） was synthesized from carbon dioxide （GO2 ）, phenol and carbon tetrachlonde （ CCI4 ） catalyzed by Lewis acid ZnC12 in the presence of co-catalyst. The effect of the amounts of catalyst and co-catalyst was investigated. The catalytic activity of ZnC12 did not get improved by the addition of Bu4NBr, Cs2CO3 or K2CO3, while trifluoromethanesulfonic acid （CF3 SO3 H） was an effective co-catalyst. The yield of DPC was significantly enhanced in the presence of CF3 SO3 H, which increased from 2.2% to 17% with identical amount of ZnCI2. The products in the reaction mixture were identified by gas chromatograph mass spectrometer （GC-MS）. Phenyl ehloroformate, phenyl salicytate and bis（ 2-hydroxyphenyl ） ketone were detected in addition to the target product DPC. Possible mechanisms for the formation of DPC and by-products were proposed based on GC-MS analysis.

关 键 词：CO2 苯酚 碳酸二苯酯 气相色谱-质谱联用 反应机理 

分 类 号：X13[环境科学与工程—环境科学]