基于密度泛函理论的羟胺阻聚剂的筛选与应用  

Screening and application of hydroxylamines as inhibitors based on density functional theory

作　　者：唐亚芳 黄占凯[2] 赵甲[2] 何艳贞 赵福利 张春丽[2] 刘红光[2] 韩恩山[1] TANG Yafang;HUANG Zhankai;ZHAO Jia;HE Yanzhen;ZHAO Fuli;ZHANG Chunli;LIU Hongguang;HAN Enshan(School of Chemical Engineering and Technology,Hebei University of Technology,Tianjin 300130,China;Refinery Additives Laboratory,CenerTech Tianjin Chemical Research and Design Institute Limited Company,Tianjin 300130,China)

机构地区：[1]河北工业大学化工学院,天津300130 [2]中海油天津化工研究设计院炼油与化工助剂实验室,天津300130

出　　处：《化工进展》2021年第10期5670-5677,共8页Chemical Industry and Engineering Progress

摘　　要：研究了羟胺类阻聚剂的阻聚作用与其分子有关电子结构性质之间的关系。用密度泛函理论(DFT)B3LYP方法在6-31g(d)基组水平上得到了5种羟胺分子的前线轨道图及其能量值,并计算了与羟胺阻聚作用有关的电子结构性质。通过理论分析和实验相结合的方法,发现了阻聚作用强的羟胺分子具有HOMO轨道电子离域度高、能隙小、分子硬度高、电负性和亲电性低等特点。且在这几种影响羟胺阻聚作用的因素中,能隙、分子硬度、电负性和亲电性的影响更大,HOMO轨道电子离域度影响较小。通过拟合阻聚诱导期与分子亲电性之间的曲线,发现二者之间存在线性关系。此外,羟胺与2-仲丁基-4,6-二硝基酚(DNBP)的协同作用也可以用DFT计算加以解释,进一步证明了DFT计算对阻聚剂的选择和优化具有重要作用。The relationship between the polymerization inhibition of hydroxylamines in styrene and their electronic properties was studied.The energy of their frontier orbitals were caculated at the density functional B3LYP level using the 6-31g(d)basis set,and the electronic properties related to polymerization inhibition were also calculated.Through a combination of theoretical analysis and experiments,it was found that hydroxylamines with good polymerization inhibition on styrene had the characteristics of high electron delocalization of HOMO,low bond gap,high molecular hardness,low electronegativity and electrophilicity.Among these factors,bond gap,molecular hardness,electronegativity and electrophilicity were more important than the electron delocalization of HOMO.It could be found that there was a linear relationship between the induction period and the molecular electrophilicity.In addition,the synergistic effect of hydroxylamine and DNBP(2-sec-butyl-4,6-dinitrophenol)could also be explained by density functional theory(DFT)calculation,which further proved that DFT calculation played an important role in the screening and application of polymerization inhibitors.

关 键 词：阻聚效果 羟胺 密度泛函理论 前线轨道 

分 类 号：TQ9[化学工程]