双咪唑啉缓蚀剂的缓蚀性能评价
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摘要
以丁二酸与二乙烯三胺为原料合成了双咪唑啉(BIM),再与氯化苄季铵化后得到双咪唑啉季铵盐(BIMI)。采用静态失重法和电化学方法评价了BIMI缓蚀剂在质量分数为15%的HCl溶液中对N80碳钢的缓蚀性能,探讨了其在N80碳钢表面的吸附行为,并与合成的咪唑啉季铵盐(SIMI)缓蚀剂作比较。应用Gaussian 03W程序,密度泛函理论(DFT)的B3LYP/6-311G*方法对两种咪唑啉进行了结构优化,分别得到了两者的稳定构型及相关量化参数,同时对两种分子在Fe(001)晶面的吸附进行了分子动力学模拟。结果表明:双咪唑啉缓蚀剂的缓蚀效果要明显优于单咪唑啉缓蚀剂的,当其浓度为3.0mmol/L时,缓蚀率达到93.30%,而同样条件下,单咪唑啉缓蚀剂的缓蚀率仅为76.93%。两种缓蚀剂在金属表面的吸附服从Langmuir吸附等温式,属于以化学吸附为主的混合吸附。量子化学计算及分子动力学模拟,从分子水平解释了两种缓蚀剂的缓蚀性能差异,其结果与试验结果一致。
Bis-imidazoline(BIM)was synthesized with butanedioic acid and diethylenetriamine as raw materials.And bis-imidazoline quaternary ammonium salt(BIMI),a novel corrosion inhibitor,was obtained through the reaction of BIM with benzyl chloride.The corrosion inhibition of BIMI inhibitor to N80 steel in 15%(mass)HCl solution was investigated via static weight loss method and electrochemical method,respectively.And the adsorption behavior of BIMI on N80 steel surface was also studied.Synthesized single-imidazoline quaternary ammonium salt(SIMI)was also studied as a corrosion inhibitor in comparison of BIMI.Gaussian 03 W program and density functional theory(DFT)B3 LYP/6-311 G* method were used to optimize the structure of two kinds of imidazoline,and the stable configuration and related quantum-chemical parameters were obtained respectively.And molecular dynamics(MD)simulation of the adsorption of two molecules on Fe(001)plane was also carried out.The results show that the inhibition efficiency of BIMI inhibitor was significantly better than that of SIMI.The inhibition efficiency of BIMI reached 93.30% when the concentration of inhibitor was 3.0 mmol/L,while that of SIMI was only76.93% under the same condition.The adsorption of two inhibitors on the metal surface obeyed the Langmuir adsorption isotherm and was a mixed adsorption based on chemical adsorption.The differences between these two corrosion inhibitors were well explained from molecular level by quantum-chemistry calculation and MD simulation,which had corresponding results with testing.
Bis-imidazoline(BIM)was synthesized with butanedioic acid and diethylenetriamine as raw materials.And bis-imidazoline quaternary ammonium salt(BIMI),a novel corrosion inhibitor,was obtained through the reaction of BIM with benzyl chloride.The corrosion inhibition of BIMI inhibitor to N80 steel in 15%(mass)HCl solution was investigated via static weight loss method and electrochemical method,respectively.And the adsorption behavior of BIMI on N80 steel surface was also studied.Synthesized single-imidazoline quaternary ammonium salt(SIMI)was also studied as a corrosion inhibitor in comparison of BIMI.Gaussian 03 W program and density functional theory(DFT)B3 LYP/6-311 G* method were used to optimize the structure of two kinds of imidazoline,and the stable configuration and related quantum-chemical parameters were obtained respectively.And molecular dynamics(MD)simulation of the adsorption of two molecules on Fe(001)plane was also carried out.The results show that the inhibition efficiency of BIMI inhibitor was significantly better than that of SIMI.The inhibition efficiency of BIMI reached 93.30% when the concentration of inhibitor was 3.0 mmol/L,while that of SIMI was only76.93% under the same condition.The adsorption of two inhibitors on the metal surface obeyed the Langmuir adsorption isotherm and was a mixed adsorption based on chemical adsorption.The differences between these two corrosion inhibitors were well explained from molecular level by quantum-chemistry calculation and MD simulation,which had corresponding results with testing.
引文
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[14]雷武,赵维,夏明珠,等.有机缓蚀剂定量构效与活性相关的热力学参数量子化学计算值与缓蚀效率的QSAR研究[J].计算机与应用化学,2003,20(1):139-142.
[15] GECE G.The use of quantum chemical methods in corrosion inhibitor studies[J].Corrosion Science,2008,50(11):2981-2992.
[16]张军,于维钊,燕友果,等.咪唑啉缓蚀剂在Fe(001)表面吸附行为的分子动力学模拟[J].物理化学学报,2010,26(5):1385-1390.
[17] ACHARY G,NAIK Y A,KUMAR S V,et al.An electroactive co-polymer as corrosion inhibitor for steel in sulphuric acid medium[J].Applied Surface Science,2008,254(17):5569-5573.
[18] DONER A,SOLMAZ R,OZCAN M,et al.Experimental and theoretical studies of thiazoles as corrosion inhibitors for mild steel in sulphuric acid solution[J].Corrosion Science,2011,53(9):2902-2913.
[19] OLIVARES-XOMETL O, LIKHANOVANV,DOMINGUEZ-AGUILAR M A,et al.Synthesis and corrosion inhibition ofα-amino acids alkylamides for mild steel in acidic environment[J].Materials Chemistry&Physics,2008,110(2/3):344-351.
[20] FUCHS-GODEC R,DOLECEK V.An effect of sodium dodecylsufate on the corrosion of copper in sulphuric acid media[J].Colloids Surfaces A:Physicochemical&Engineering Aspects,2004,244(1/3):73-76.
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[22] MU G N,LI X M,LIU G H.Synergistic inhibition between tween 60and NaCl on the corrosion of cold rolled steel in 0.5Msulfuric acid[J].Corrosion Science,2005,47(8):1932-1952.
[23] OUTIRITE M,LAGRENEE M,LEBRINI M,et al.AC impedance,X-ray photoelectron spectroscopy and density functional theory studies of 3,5-bis(n-pyridyl)-1,2,4-oxadiazoles as efficient corrosion inhibitors for carbon steel surface in hydrochloric acid solution[J].Electrochimica Acta,2010,55(5):1670-1681.
[24]胡松青,胡建春,石鑫,等.咪唑啉衍生物缓蚀剂的定量构效关系及分子设计[J].物理化学学报,2009,25(12):2524-2530.
[25] BEREKET G,HUR E.Quantum chemical studies on some imidazole derivatives as corrosion inhibitors for iron in acidic medium[J].Journal of Molecular Structure:Theochem,2002,578(1/3):79-88.
[26] PEARSON R G. Absolute electronegativityand hardness:application to inorganic chemistry[J].Inorganic Chemistry,1988,27(4):734-740.
[27]陈钧,白林,宋纪蓉,等.咪唑啉缓蚀剂构效关系的量子化学研究[J].计算机与应用化学,2012,29(8):1009-1013.
[28] LUKOVITS I,KALMAN E,ZUCCHI F.Corrosion inhibitors-correlation between electronic structure and efficiency[J].Corrosion,2001,57(1):3-8.
[29] AHAMAD I,PRASAD R,QURAISHI M A.Inhibition of mild steel corrosion in acid solution by pheniramine drug:experimental and theoretical study[J].Corrosion Science,2010,52(9):3033-3041.
[2]李言涛,王路遥,史德青,等.油气田用咪唑啉缓蚀剂的研究进展[J].材料保护,2011,44(12):50-54.
[3]黄光团,甄库,陆柱.新型咪唑啉衍生物油田注水缓蚀剂的研究[J].腐蚀与防护,2004,25(2):50-52.
[4]余宗学,梁灵,何毅,等.新型抗温抗酸含磺酸基咪唑啉缓蚀剂的合成及其性能[J].材料保护,2015,48(5):27-30.
[5] GRANESE S L,ROSALES B M,OVIEDO C,et al.The inhibition action of heterocyclic nitrogen organic compounds on Fe and steel in HCl media[J].Corrosion Science,1992,33(9):1439-1453.
[6]宋伟伟,张静,杜敏.双季铵盐类缓蚀剂的研究进展[J].化工进展,2011,30(4):842-847.
[7]张光华,强轶,葛磊,等.新型双子咪唑啉季铵盐缓蚀剂的合成及其性能[J].材料保护,2013,46(3):15-17.
[8]尹成先,阮林华,丁万成,等.抗高温CO2腐蚀固体缓蚀剂的研究[J].材料保护,2006,39(2):1-3.
[9]梅平,胡玲莉,高秋英,等.酸化用双咪唑啉季铵盐缓蚀剂的合成与性能评价试验[J].石油天然气学报,2007,29(4):140-143.
[10]潘成松,王霞,李刚,等.油气田酸化用缓蚀剂双咪唑啉季铵盐的合成及评价[J].精细石油化工进展,2008,9(11):4-7.
[11]蒋斌,张静,杜敏,等.含咪唑啉环不对称双季铵盐的合成及其缓蚀性能[J].精细化工,2009,26(8):760-763.
[12]付薇,梁亮,郑敬生,等.Gemini型咪唑啉双季铵盐金属缓蚀剂的合成及其性能[J].应用化学,2009,26(12):1422-1427.
[13]李华金,俞斌.双咪唑啉衍生物缓蚀剂的合成与缓蚀研究[J].化工时代,2009,23(6):15-17.
[14]雷武,赵维,夏明珠,等.有机缓蚀剂定量构效与活性相关的热力学参数量子化学计算值与缓蚀效率的QSAR研究[J].计算机与应用化学,2003,20(1):139-142.
[15] GECE G.The use of quantum chemical methods in corrosion inhibitor studies[J].Corrosion Science,2008,50(11):2981-2992.
[16]张军,于维钊,燕友果,等.咪唑啉缓蚀剂在Fe(001)表面吸附行为的分子动力学模拟[J].物理化学学报,2010,26(5):1385-1390.
[17] ACHARY G,NAIK Y A,KUMAR S V,et al.An electroactive co-polymer as corrosion inhibitor for steel in sulphuric acid medium[J].Applied Surface Science,2008,254(17):5569-5573.
[18] DONER A,SOLMAZ R,OZCAN M,et al.Experimental and theoretical studies of thiazoles as corrosion inhibitors for mild steel in sulphuric acid solution[J].Corrosion Science,2011,53(9):2902-2913.
[19] OLIVARES-XOMETL O, LIKHANOVANV,DOMINGUEZ-AGUILAR M A,et al.Synthesis and corrosion inhibition ofα-amino acids alkylamides for mild steel in acidic environment[J].Materials Chemistry&Physics,2008,110(2/3):344-351.
[20] FUCHS-GODEC R,DOLECEK V.An effect of sodium dodecylsufate on the corrosion of copper in sulphuric acid media[J].Colloids Surfaces A:Physicochemical&Engineering Aspects,2004,244(1/3):73-76.
[21] TEBBJI K,FASKA N,TOUNSI A,et al.The effect of some lactones as inhibitors for the corrosion of mild steel in 1 M hydrochloric acid[J].Materials Chemistry&Physics,2007,106(2/3):260-267.
[22] MU G N,LI X M,LIU G H.Synergistic inhibition between tween 60and NaCl on the corrosion of cold rolled steel in 0.5Msulfuric acid[J].Corrosion Science,2005,47(8):1932-1952.
[23] OUTIRITE M,LAGRENEE M,LEBRINI M,et al.AC impedance,X-ray photoelectron spectroscopy and density functional theory studies of 3,5-bis(n-pyridyl)-1,2,4-oxadiazoles as efficient corrosion inhibitors for carbon steel surface in hydrochloric acid solution[J].Electrochimica Acta,2010,55(5):1670-1681.
[24]胡松青,胡建春,石鑫,等.咪唑啉衍生物缓蚀剂的定量构效关系及分子设计[J].物理化学学报,2009,25(12):2524-2530.
[25] BEREKET G,HUR E.Quantum chemical studies on some imidazole derivatives as corrosion inhibitors for iron in acidic medium[J].Journal of Molecular Structure:Theochem,2002,578(1/3):79-88.
[26] PEARSON R G. Absolute electronegativityand hardness:application to inorganic chemistry[J].Inorganic Chemistry,1988,27(4):734-740.
[27]陈钧,白林,宋纪蓉,等.咪唑啉缓蚀剂构效关系的量子化学研究[J].计算机与应用化学,2012,29(8):1009-1013.
[28] LUKOVITS I,KALMAN E,ZUCCHI F.Corrosion inhibitors-correlation between electronic structure and efficiency[J].Corrosion,2001,57(1):3-8.
[29] AHAMAD I,PRASAD R,QURAISHI M A.Inhibition of mild steel corrosion in acid solution by pheniramine drug:experimental and theoretical study[J].Corrosion Science,2010,52(9):3033-3041.