摘要
采用气相色谱-质谱联用技术，对超临界CO2中苯酚氧化羰基化反庸合成碳酸二苯酯（DPC）的产物进行了定性分析。分析结果表明，与以二氯甲烷为溶剂的苯酚氧化羰基化反应不同，在超临界CO2中该反应的主要副产物是o-亚苯基碳酸酯。通过对反应物系的分析认为，这是由于苯酚首先在Cu化合物的催化下发生邻位氧化反应得到邻苯二酚，邻苯二酚再与超临界CO2，发生羰基化反应得到o-亚毕基碳酸酯。采用气相色谱井利用外标法对反应混合物中的DPC和苯酚进行了定量分析。DPC和苯酚的外标曲线相关系数分别为0．99836和0．99903，方法的标准偏差分别为8．9％和7．7％，回收率分别为94．3％-105．3％和92．0％～105．0％。该方法重现性好，适用于超临界CO2中苹酚氧化羰基化反应产物DPC和反应物苯酚的分析。
Qualitative analysis of products and by-products obtained by oxidative carbonylation of phenol to diphenyl carbonate （DPC） in supercritical CO2 was carded out by means of GC-MS. Differently from traditional oxidative carbonylaion of phenol in CH2 Cl2 solvent, o-phenylene carbonate was identified as main by-product when reaction was carded out in supercritical CO2. It was found that o-phenylene carbonate was carbonylation product of supercritical CO2 and catechol which was derived from ortho oxidation of phenol on copper compound catalyst. DPC and phenol in reaction system were quantitatively analyzed by means of GC with external standard method. Correlation coefficients of external standards for DPC and phenol were 0. 998 36 and 0.999 03 ,respectively. Their relative standard deviations were 8.9% and 7.7% ,respectively. 94.3% - 105.3% DPC and 92.0% - 105.0% phenol could be recovered. This method was reliable for quantitative analysis of diphenyl carbonate and phenol obtained by oxidative carbonylation of phenol in supercritical CO2.
出处
《石油化工》
CAS
CSCD
北大核心
2006年第3期284-288,共5页
Petrochemical Technology
基金
国家自然科学基金资助项目(20176008)
关键词
碳酸二苯酯
氧化羰基化
超临界二氰化碳
分析
苯酚
diphenyl carbonate
oxidative carbonylation
supercritical dioxygen
analysis
phenol
