文献类型：期刊文献

中文题名：基于密度泛函理论的甲基芳烃液相氧化反应活性分析

英文题名：Reactivity analysis of methyl aromatics in liquid phase oxidation based on density functional theory

作者：袁方[1];周绪振[2];吕全明[1];孙伟振[1];赵玲[1,3]

机构：[1]华东理工大学化学工程联合国家重点实验室,上海200237;[2]江苏海伦石化有限公司,江苏无锡214400;[3]新疆大学化学化工学院,新疆乌鲁木齐830046

年份：2022

卷号：51

期号：9

起止页码：1064

中文期刊名：石油化工

外文期刊名：Petrochemical Technology

收录：CSTPCD;;Scopus;北大核心:【北大核心2020】；CSCD:【CSCD2021_2022】；

语种：中文

中文关键词：甲基芳烃;液相氧化;甲基氧化活性;密度泛函理论

外文关键词：methyl aromatics;liquid phase oxidation;methyl oxidation reactivity;density functional theory

摘要：采用密度泛函理论方法并考虑溶剂效应,对具有不同甲基芳烃的液相氧化反应活性进行了研究;通过在wB97XD/6-311G(d)基组水平上进行过渡态搜索计算,得到了反应溶剂中甲基芳烃液相氧化链引发阶段和链传递阶段所涉及的反应物和产物的最优几何构型和分子能量;并通过Hammett方程估算了甲基芳烃上甲基的相对反应活性。计算结果表明,芳烃上甲基的氧化活性从高到低顺序依次为:均四甲苯>连四甲苯>对二甲苯>间二甲苯>甲苯;且随着甲基数量的增多,不同芳烃同分异构体的甲基氧化活性差异减小;当对二甲苯上第一个甲基被氧化为羧基之后,由于后者的强吸电子效应第二个甲基的氧化活性降低为原来的1/10;随着四甲基芳烃上甲基被依次氧化为羧基,剩余甲基的活性一般降低为原先的1/8~1/5。
The liquid-phase oxidation reactivity of different methyl aromatics was investigated using density functional theory with the consideration of solvent effects.By transition state search calculation at the wB97XD/6-311G(d)basis set level,the optimal geometric configurations and molecular energies of reactants and products involved in the chain initiation stage and chain transfer stage of liquid-phase oxidation of methyl aromatics in the reaction solvent were obtained.The relative reactivity of methyl on methyl aromatics was estimated by Hammett equation.The calculation results show that the oxidation activity of methyl on different aromatics follows the order of durene>prehnitene>p-xylene>m-xylene>toluene.And the difference of oxidation reactivity of methyl in different aromatic isomers decreases with the increase of methyl number.When the first methyl group of p-xylene is oxidized to carboxyl group,the oxidation reactivity of the second methyl group is reduced to 1/10 of the original due to the strong electron withdrawing effect of the carboxyl group,and as the methyl groups of durene or prehnitene are sequentially oxidized to carboxyl groups,the reactivity of the remaining methyl group is generally reduced to 1/8-1/5 of the former.