屏蔽酚分子结构与高温抗氧化性能关系研究  

Relationship Between Molecular Structure and High-temperature Antioxidation Performance of Hindered Phenols

作　　者：苏朔 赵毅 于乐 龙军 Su Shuo;Zhao Yi;Yu Le;Long Jun(SINOPEC Research Institute of Petroleum Processing,Beijing 100083,China;Beijing University of Chemical Technology,Beijing 100029,China)

机构地区：[1]中石化石油化工科学研究院有限公司,北京100083 [2]北京化工大学,北京100029

出　　处：《山东化工》2024年第15期39-45,49,共8页Shandong Chemical Industry

基　　金：中国石油化工股份有限公司重点科技项目(115080)。

摘　　要：分别采用热失重法和加压差示扫描量热法考察了不同结构屏蔽酚的热稳定性及其高温抗氧化性能,采用基于密度泛函理论的分子模拟方法计算了屏蔽酚分子的抗氧化特征参数,运用遗传算法建立了屏蔽酚分子结构参数与高温氧化诱导期之间的定量关系方程。结果表明,相对分子质量是影响屏蔽酚热稳定性的关键因素;所建立的定量结构与性能关系方程具有明确的物理化学意义,交叉检验相关系数R CV^(2)为0.914,具有较好的预测能力;揭示出S原子Mulliken负电荷数、O—H键解离能和分子最高占据轨道能量是影响屏蔽酚高温氧化性能的关键分子结构特征参数,且三个参数影响高温抗氧化性能的权重大小依次降低。从改善抗氧化性能的角度出发,应该设计开发具备如下结构特征的含硫屏蔽酚:S原子Mulliken负电荷较多、O—H键解离能较低、分子最高占据轨道能量较高。这为新结构高性能屏蔽酚类抗氧剂产品的设计开发指明了方向。The thermal stability and high temperature oxidation resistance of hindered phenols with different structures in lube base oils were investigated by thermogravimetric analysis(TGA)and high-pressure differential scanning calorimetry(PDSC),respectively.The antioxidation characteristic parameters of hindered phenols were calculated by ab initio algorithm of quantum chemistry,and the quantitative relationship between molecular structure parameters of hinderedg phenols and high temperature oxidation induction period was established by genetic algorithm.The results show that the relative molecular weight is the key factor affecting the thermal stability of hindered phenols.The established quantitative structure-property relationship equation has clear physical and chemical significance,and the cross-test correlation coefficient R CV^(2) is 0.914,which has good prediction ability.Bond dissociation energy(BDE)of O—H,mulliken charges of S atoms(Q S),and energy of molecular maximum occupied orbital(E HOMO)are the three key molecular characteristic parameters affecting the high-temperature antioxidant performance of hindered phenols.The order in which these three parameters influence the high-temperature antioxidant performance of hindered phenols is as follows:Q S>BDE(O—H)>E HOMO.In order to improve the antioxidant activity,sulfur-containing hindered phenols should be designed and developed with the following structural characteristics:more negative Mulliken charges of S atoms,lower dissociation energy of O—H bonds and higher energy of molecular maximum occupied orbital.This indicates the direction for the design and development of high performance phenolic antioxidant products with new structure.

关 键 词：屏蔽酚 抗氧化性能 分子模拟 遗传算法 定量结构与性能关系 

分 类 号：TQ317.6[化学工程—高聚物工业]