基于密度泛函理论的羟胺阻聚剂的筛选与应用

doi:10.16085/j.issn.1000-6613.2020-2164

摘要/Abstract

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。

关键词: 阻聚效果, 羟胺, 密度泛函理论, 前线轨道

Abstract:

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.

Key words: polymerization inhibition, hydroxylamine, density functional theory (DFT), frontier orbital

中图分类号:

唐亚芳, 黄占凯, 赵甲, 何艳贞, 赵福利, 张春丽, 刘红光, 韩恩山. 基于密度泛函理论的羟胺阻聚剂的筛选与应用[J]. 化工进展, 2021, 40(10): 5670-5677.

TANG Yafang, HUANG Zhankai, ZHAO Jia, HE Yanzhen, ZHAO Fuli, ZHANG Chunli, LIU Hongguang, HAN Enshan. Screening and application of hydroxylamines as inhibitors based on density functional theory[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5670-5677.

图/表 12

图1 Mayo提出的苯乙烯聚合机理

图2 化合物1~5和空白组在阻聚40min和80min后的聚合转化率

表1 5种不同羟胺的诱导期时间

化合物	诱导期/min
1	23
2	14
3	19
4	5
5	10

表2 化合物1~化合物5的前线轨道

化合物	E_HOMO/eV	E_LUMO/eV
1	-6.6635	1.3695
2	-6.4853	0.1395
3	-6.5013	0.2989
4	-6.1431	0.5734
5	-6.1986	0.2007

表3 化合物1~5的能隙与分子硬度

化合物	能隙/eV	η /eV
1	-8.0330	4.0165
2	-6.6248	3.3124
3	-6.8003	3.4001
4	-5.5697	2.7849
5	-5.9979	2.9989

图3 阻聚转化率与能隙和分子硬度的关系

图4 羟胺的阻聚机理

表4 化合物1~5的电负性（μ）和亲电性（ω）

化合物	μ/eV	ω/eV
1	2.6470	0.8722
2	3.1729	1.5196
3	3.1012	1.4143
4	3.3582	2.0248
5	3.1997	1.7069

图5 阻聚转化率与电负性和亲电性的关系

图6 羟胺亲电性与阻聚诱导期的线性关系

图7 N,N-二乙基羟胺的前线轨道图及与其阻聚相关的电子结构性质参数

图8 N,N-二乙基羟胺与DNBP协同作用

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