摘要
近年来，喹啉类衍生物因具有五元含氮杂环结构和低毒性，在缓蚀剂领域受到广泛关注。但是从报道的文献看，现今合成的喹啉类衍生物的缓蚀效率依旧不高，同时毒性的研究十分缺乏，寻求高效低毒型喹啉类缓蚀剂依旧是现今的研究热点。
本文以喹啉和苄氯为原料，合成了两种喹啉类衍生物：5-苯并喹啉（BQ）和6-（喹啉-5-亚甲基）苯-1,2,3,4,5-磺酸（QBPA），并对其进行了核磁和红外光谱表征。通过毒性预测软件T.E.S.T对近年来发表的几种典型缓蚀剂和本文合成的缓蚀剂进行了毒性预测。通过失重和电化学实验研究了BQ和QBPA在1 M HCl中对碳钢和在0.5 M H2SO4中对纯铜的缓蚀作用，结合量子化学计算和分子动力学模拟方法对缓蚀剂的缓蚀机理进行了研究。主要研究结果如下：
①利用T.E.S.T软件对苯并噻唑类、苯并咪唑类、吡啶类、希夫碱类、含硫杂环化合物、BQ和QBPA等十一（类）种缓蚀剂的健康毒性（Ames致畸变性、发育毒性、小鼠经口LD50）和生态毒性(大型蚤LC50、96h黑头呆鱼LC50)进行预测，发现只有BQ和QBPA既无健康毒性同时生态毒性很低，是环境友好型缓蚀剂。
②BQ和QBPA对碳钢在1 M HCl中的腐蚀具有优异的缓蚀效果，且随缓蚀剂浓度增加而增强，在1 mM浓度下达到缓蚀效率：96.54%（BQ）和98.03%（QBPA）。BQ和QBPA在碳钢上的吸附符合Langmuir吸
附模型，均是物理化学混合吸附，且QBPA更倾向于化学吸附。电化学测试表明BQ和QBPA均是阴阳极混合型缓蚀剂。
③BQ和QBPA对纯铜在0.5 M H2SO4中的腐蚀具有优异的缓蚀效果，在1 mM 浓度下达到缓蚀效率：96.7%（BQ）和98.3%（QBPA）。极化曲线测试表明两种缓蚀剂均是阴极型缓蚀剂，明显阻碍了氧气从溶液本体向金属表面的传递；阻抗谱测试表明BQ和QBPA的加入没有显著改变纯铜的腐蚀机制，主要是通过占据金属表面的活性位点达到缓蚀作用。在缓蚀剂浓度较高时Warburg阻抗消失，说明在阴极反应中氧气的传质过程不再是主要影响因素。BQ和QBPA在纯铜上的吸附符合Langmuir吸附模型，且均以化学吸附为主。
④研究发现，对1 M HCl中碳钢和0.5 M H2SO4中纯铜的缓蚀效果QBPA均优于BQ。量子化学计算发现BQ的HOMO和LUMO轨道集中在喹啉环上，而QBPA的HOMO轨道在喹啉环和相邻的亚甲基上，LUMO轨道在磺酸基及与之相连的苯环上，因此QBPA比BQ有更多的吸附位点，缓蚀效果强于BQ。
关键词：喹啉类缓蚀剂，T.E.S.T毒性预测，电化学测试，量子化学计算
ABSTRACT
Quinoline derivatives have been attracted extensive attention in corrosion inhibitor rearch field owi
ng to their low toxicity and N-containing heterocyclic structure for the past few years. However, low inhibition efficiency and bare toxicity rearch decelerate quinoline derivatives development. Hence, high-efficient and low-toxic inhibitors exploring is still a hot issue.
In this thesis, two quinoline derivatives named 6-benzylquinoline (BQ) and 6-(quinolin-5-ylmethyl) benzene-1, 2, 3, 4, 5-pentasulfonic acid (QBPA) have been synthesized and characterized by 1H NMR spectroscopy and Fourier transform infrared spectroscopy. Weight loss and electrochemical measurements were implemented to investigate the inhibition performance of BQ and QBPA on mild steel in 1 M HCl and copper in 0.5 M H2SO4, respcectively. Quantum chemical calculations and molecule dynamics (MD) simulation were implemented to explain the inhibition mechanism of the two organic molecules. The main work of this thesis are as follows:falhood
①The toxicity of typical inhibitors such as benzothiazoles, imidazoles, pyridines, schiff bes, sulfur-containing heterocyclic compounds and quinoline derivatives synthesized in this essay has been calculated by T.E.S.T software. The calculation found that only BQ and QBPA belong enviornmental friendly inhibitors becau they own no health toxicity and low eco-toxicity among the inhibitors.
②QB and BQPA acted as excellent inhibitors for mild steel in 1 M HCl solution and their inhibition effi
ciency enhanceed with the increa of concentration. The maximum inhibition efficiency was 96.54% for QB and 98.03% for BQPA (obtained from EIS at 298K) at 1 mM, respectively. The adsorption of QB and BQPA on steel surface obeyed Langmuir adsorption isotherm with a mixed physisorption and chemisorption mechanism. Electrochemical results indicated that QB and BQPA performed as both anode and cathodic type inhibitors without changing hydrogen evolution’s mechanism. And the addition of inhibitors mainly hinders the active sites on steel surface.
③QB and BQPA acted as excellent inhibitors for copper in 0.5 M H2SO4 solution and the maximum inhibition efficiency was 96.7% for QB and 98.3% for BQPA at 1 mM, respectively. Potentiodynamic polarization results indicated that QB and BQPA performed as cathodic type inhibitor and mainly impeded the diffusion process of oxygen. Electrochemical impedance spectroscopy showed that the addition of inhibitors mainly
重庆大学硕士学位论文
hindered the active sites on steel surface. And the adsorption of QB and BQPA on copper surface obeyed Langmuir adsorption isotherm with chemisorption mechanism.
④Results of all testing methods showed that QBPA owned a better inhibition performance than BQ. I
t could be explained by Quantum chemical calculations results. HOMO and LOMO of BQ were almost localized evenly on the quinoline ring and benzyl group (linked to quinoline ring). By contrast, HOMO of QBPA was distributed in quinoline ring while its LUMO was located in the rest of molecule structure. Hence, rational assumption can be propod that QBPA includes more adsorption sites than BQ, issuing in a stronger adsorption capability.
Keywords:Quinoline inhibitors, T.E.S.T toxicity estimation, Electrochemical testing, Quantum chemical calculations
IV
目录
目录
中文摘要 ................................................................................................................................... I 英文摘要 ................................................................................................................................ III 1 绪论.. (1)
1.1 缓蚀剂概述 (1)
1.1.1 缓蚀剂分类 (1)
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1.1.2 缓蚀机理 (1)
1.1.3 常用研究手段 (3)
1.2 酸性介质中碳钢缓蚀剂研究现状 (3)
1.2.1 盐酸介质中的缓蚀剂 (4)customary
1.2.2 其他酸性介质中的缓蚀剂 (4)
1.3 酸性介质中铜缓蚀剂研究现状 (5)
1.4 喹啉类缓蚀剂研究进展 (5)
1.5 毒性预测 (6)
1.5.1 QSAR概述 (6)
宝宝怎么学英语1.5.2 T.E.S.T软件简介 (6)
1.5.3 毒性预测终点 (7)
1.5.4 T.E.S.T软件中的QSAR方法论 (7)
1.6 本文研究内容 (8)
2 两种喹啉类缓蚀剂的合成与表征 (9)
2.1 实验仪器及药品 (9)
over the love2.1.1 实验药品 (9)
2.1.2 实验仪器 (9)
2.2 喹啉类缓蚀剂的合成 (9)
2.2.1 合成原理 (9)
2.2.2 合成步骤 (10)
2.3 喹啉类缓蚀剂的结构表征 (10)
2.3.1核磁共振氢谱 (10)
2.3.2傅里叶红外光谱 (11)
2.4 本章小结 (12)
3 缓蚀剂毒性评估研究 (13)
国字脸男生适合什么发型3.1 研究背景 (13)
V
重庆大学硕士学位论文
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3.2 参数设置 (13)
3.3 结果与讨论 (14)
3.3.1 健康毒性 (14)
3.3.2 生态毒性 (15)
3.3.3 T.E.S.T软件外部统计验证 (16)
relationship是什么意思
3.3 本章小结 (18)
4 盐酸介质中BQ和QBPA对碳钢的缓蚀性能研究 (19)
4.1 研究背景 (19)
4.2 实验材料与研究方法 (19)
4.2.1 主要实验仪器和试剂 (19)
4.2.2 金属材料 (20)
4.2.3 失重实验 (20)
4.2.4 电化学实验 (21)
4.2.5 表面分析 (21)
4.3 结果与讨论 (22)
4.3.1 失重实验 (22)l carnitine
4.3.2 吸附行为的研究 (25)
popc4.3.3 动电位极化曲线 (27)
4.3.4 电化学交流阻抗谱 (30)
4.3.5 扫描电镜分析 (34)
4.3.6 原子力显微镜分析 (34)
4.4 本章小结 (35)
5 硫酸介质中BQ和QBPA对纯铜的缓蚀性能研究 (37)
5.1 研究背景 (37)
5.2 实验材料与研究方法 (37)
5.2.1 主要实验仪器和试剂 (37)
5.2.2 金属材料 (37)
5.2.3 电化学实验与表面分析 (37)
5.3 结果与讨论 (37)
5.3.1 动电位极化曲线 (37)
5.3.2 电化学交流阻抗谱 (42)
5.3.3 吸附行为的研究 (44)
5.3.4 扫描电镜分析 (45)
5.3.5 原子力显微镜分析 (46)
VI
