氧化羰基化法合成碳酸二苯酯的定性和定量分析

Qualitative and Quantitative Determination of the Products Synthesized by Oxidative Carbonylation of Phenol with CO and O_2

采用溶胶凝胶法合成铜、钴、锰混合氧化物作为载体,负载氯化钯催化氧化羰基化合成碳酸二苯酯,利用气相色谱-质谱联用技术对产物进行了定性分析,用气相色谱内外标相结合的方法进行了定量分析。定性结果表明,副产乙酸苯酯、三丁基铵、1-安息香酸基-2-羟基苯酯和对溴苯基碳酸苯酯,并在此基础上提出生成机理;定量结果表明,苯酚和苯酚/碳酸二苯酯（DPC）线性回归标准方程的相关系数分别为0.99883和0.99869,DPC和苯酚的相对标准偏差分别为2.18%和5.44%,回收率分别为98.38%-103.69%和98.33%-101.42%,该方法重现性好,适用于此催化体系中氧化羰基化反应目标产物DPC和反应物苯酚的分析。

The products of the direct synthesis of diphenyl carbonate with heterogeneous catalytic system were identified by GC-MS, which used copper cobalt manganese mixed oxides as the support. The quantitative determination was carried out by GC with external and internal standard methods. The main side-products has been found to be phenyl acetate, tributylamine, 1-benzoic acid-2-hydroxyphenyl ester and p-bromophenyl carbonic acid phenyl ester, and the possible mechanism of products is also proposed. The correlation coefficients for phenol and the proportion of phenol and DPC are 0.998 83 and 0.998 69, respectively. The relative standard deviations of DPC and phenol are 2.18% and 5.44%, respectively. 98.38%-103.69% DPC and 98.33%-101.42% phenol could be recovered. This method is reliable for quantitative analysis of DPC and phenol obtained by oxidative earbonylation of phenol with CO and O2 in the catalytic system.