影响烷基芳烃黏度的内在结构因素探究
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摘要
利用多种分子模拟方法对78种不同结构烷基芳烃分子分别计算了331种微观结构参数(包括前线轨道能量、电荷分布、表面积、偶极矩电子结构参数、几何结构参数和分子拓扑指数)。采用遗传算法(GFA)将这些微观结构参数与烷基芳烃的100℃黏度进行回归分析,构建烷基芳烃100℃黏度与其分子结构参数之间的定量关系方程。方程相关系数平方为0.935,交叉检验相关系数平方为0.921,具有较高的可靠性和预测能力。该方程揭示了烷基芳烃的前线轨道能量间隙、分子体积和可旋转化学键数量是影响其100℃黏度高低的主要结构因素。烷基芳烃前线轨道能量间隙越窄,黏度越高;分子尺寸越大,黏度越高;可旋转化学键越少,黏度越高。依据这三个结构参数,利用构建的定量关系方程,能够对烷基苯、烷基萘等芳烃的100℃黏度进行较为准确地预测,对于设计与优化具有理想黏度值的烷基芳烃基础油具有一定的指导意义和价值。
Various structural and electronic descriptors of 78 kinds of alkylaromatics, such as charge distribution,HOMO and LUMO Eigenvalues, dipole, molecular surface area, molecular volume, etc., were calculated by using molecular simulation method, and many kinds of different topological descriptors were calculated as well.GFA method was selected to elucidate the relationship between the structure of alkylaromatics and their viscosity at 100℃. As a result, a quantitative equation with clear physical meanings was set up, which showed that LUMO-HOMO gap, molecular volume, and the number of rotatable bonds of alkyaromatics were the three main structural factors for their viscosity at 100℃. The narrower the LUMO-HOMO gap, the higher the viscosity, the larger the molecule, the higher the viscosity, and the less the rotatable bonds, the higher the viscosity. With these three structural descriptors, the established equation could be used to properly predict the viscosity of alkylaromatics at 100℃ with the square of correlation coefficient of 0.935 and the square of crossvalidated coefficient of 0.921, which means that the equation has a quite strong predictability for the viscosity of alkylaromatics at 100℃.
Various structural and electronic descriptors of 78 kinds of alkylaromatics, such as charge distribution,HOMO and LUMO Eigenvalues, dipole, molecular surface area, molecular volume, etc., were calculated by using molecular simulation method, and many kinds of different topological descriptors were calculated as well.GFA method was selected to elucidate the relationship between the structure of alkylaromatics and their viscosity at 100℃. As a result, a quantitative equation with clear physical meanings was set up, which showed that LUMO-HOMO gap, molecular volume, and the number of rotatable bonds of alkyaromatics were the three main structural factors for their viscosity at 100℃. The narrower the LUMO-HOMO gap, the higher the viscosity, the larger the molecule, the higher the viscosity, and the less the rotatable bonds, the higher the viscosity. With these three structural descriptors, the established equation could be used to properly predict the viscosity of alkylaromatics at 100℃ with the square of correlation coefficient of 0.935 and the square of crossvalidated coefficient of 0.921, which means that the equation has a quite strong predictability for the viscosity of alkylaromatics at 100℃.
引文
1 Rudnick LR.Alkylated aromatics in synthetics,mineral oils,and bio-based lubricants[M],Taylor&Francis,Boco Raton,2006:139-155.
2 Hessell E T,Abramshe R A.Alkylated naphthalenes as high-performance synthetic fluids[J].Journal of Synthetic Lubrication,2003,20(2):109-122.
3梁宇翔,焦广文.长链烷基萘合成工艺研究[J].石油炼制与化工,2009,40(3):22-25.LIANG Yuxiang,JIAO Guangwen.Study on the preparation of long chain alkylated naphthalenes[J].Petroleum Processing and Petrochemicals,2009,40(3):22-25.
4陈晓伟,梁宇翔.液体空间润滑剂的现状与发展[J].润滑与密封,2006(6),176-178.CHEN Xiaowei,LIANG Yuxiang.Status and Development of Liquid Space Lubricants[J].Lubrication Engineering,2006(6),176-178.
5杨士钊,胡建强,郭力,宗营.合成润滑材料[J].2012,39(1):24-26.YANG Shizhao,HU Jianqiang,GUO Li,ZONG Ying.High-performance Alkylated Naphthalene Base Stocks[J]Synthetic Lubricants,2012,39(1):24-26.
6宋上飞,刘青才,吕升阳.三氟甲磺酸催化萘烷基化研究[J].石油炼制与化工,2018,49(5):71-74.SONG Shangfei,LIU Qingcai,LV Shengyang.Alkylation of naphthalene catalyzed by trifluoromethanesulfonic acid[J].Petroleum Processing and Petrochemicals,2018,49(5):71-74.
7汪廷贵,张乐涛,蔡国星,吾满江·艾力.一种烷基萘基础油的合成及润滑性能研究[J].石油炼制与化工,2013,44(11):96-99.WANG Yangui,ZHANG Letao,CAI Huoxing,Wumanjiang Eli.Study on synthesis of alkyl naphthalene base oils and their lubricating properties,2013,44(11):96-99.
8 Joback K G,Reid R C.Estimation of pure-component properties from group-contributions[J].Chemical Engineering Communications,1987,57(2):233-243.
9 Simon R H M.Estimation of critical properties of organic compounds by the method of group contributions[J].AICHE Journal,1956,2(3):12.
10 Klincewicz K M,Reid R C.Estimation of critical properties with group contribution methods[J].AICHEJournal,1984,30(1):137-142.
11 Lyman Warren J.Handbook of chemical property estimation methods:Environmental behavior of organic compounds[M].American Chemical Society(ACS),Washington,1990.
12 Velzen D V,Cardozo R L,Langenkamp H.A liquid viscosity-temperature-chemical constitution relation for organic compounds[J].Industrial Engineering Chemistry Fundamentals,1972,11(1):20-25.
13 Allan J M,Teja A S.Correlation and prediction of the viscosity of defined and undefined hydrocarbon liquids[J].Canadian Journal of Chemical Engineering,2010,69(4):986-991.
14蔡广庆,张霖宙.烃类液体黏度的定量结构性质预测模型[J].现代化工,2018,38(7):204-207.CAI Guangqing,ZHANG Linzhou.Prediction model of QSPR for hydrocarbon liquid viscosities[J].Modern Chemical Industry,2018,38(7):204-207.
15李诚炜,田松柏,刘泽龙,刘颖荣.直馏减压馏分运动黏度的预测[J].石油学报(石油加工),2009,25(3):452-456.LI Chengwei,TIAN Songbai,LIU Zelong,LIUYingrong.Prediction of kinematic viscosity of vacuumgas oil[J].Acta Petro Lei Sinica(Petroleum Processing Section),2009,25(3):452-456.
16 Box G E,Hunter W G,Hunter J S.Statistics for experimenters:An introduction to design,data analysis,and model building,Wiley series in probability and Mathematical statistics[M].New York:John Wiley&Sons,1978:651-653.
17 Draper N R,Smith H.Applied Regression Analysis[M].Weinheim:Wiley-Interscience,1998:360-429.
18 Friedman J H.Multivariate adaptive regression splines,technical report No.102[D].Stanford:Stanford University,1990.
19汪文虎,秦延龙.烃类物理化学数据手册[M].北京:烃加工出版社,1990:82-436.WANG Wenhu,QIN Yanlong.Handbook for physical and chemical properties of hydrocarbons[M],Beijing:Hydrocarbon Processing Press,1990:82-436.
20 Wiener H.Structural determination of paraffin boiling points[J].Journal of Chemical Physicals,1947,69:17-20.
21 Muller W R.An algorithm for construction of the molecular distance matrix[J].Journal of Computational Chemistry,1987,8:170-173.
22 Stanton D,Jurs P.Development and use of charged partial surface area structural descriptors in computer assisted quantitative structure property relationship studies[J].Analytical Chemistry,1990,62:2323-2329.
23 Bonch E D.Information Theoretic Indices for Characterization of Chemical Structures[M].Chemometrics Series,Vol.5,New York:Research Studies Press Ltd.,1983:1-108.
24 Hall L H,Kier L B.Electrotopological state indices for atom types:A novel combination of electronic,topological and valence state information[J].Journal of Chemical Information and Computer Science,1995,35:1039-1045.
25 Topliss J G,Edwards R P.Chance factors in studies of quantitative structure-activity relationships[J].Journal of Medicinal Chemistry,1979,22:1238-1247.
26 Stah L L,Wold S.Progress of Medical Chemistry,Vol25[M].Amsterdam,Elsevier,1988:12-142.
27寇铨虎.影响烷烃辛烷值高低的结构因素[J].石油学报(石油加工),2010,26(4):556-559.KOU Shuanhu.Factors Affecting Octane Number of Paraffin,2010,26(4):556-559.
2 Hessell E T,Abramshe R A.Alkylated naphthalenes as high-performance synthetic fluids[J].Journal of Synthetic Lubrication,2003,20(2):109-122.
3梁宇翔,焦广文.长链烷基萘合成工艺研究[J].石油炼制与化工,2009,40(3):22-25.LIANG Yuxiang,JIAO Guangwen.Study on the preparation of long chain alkylated naphthalenes[J].Petroleum Processing and Petrochemicals,2009,40(3):22-25.
4陈晓伟,梁宇翔.液体空间润滑剂的现状与发展[J].润滑与密封,2006(6),176-178.CHEN Xiaowei,LIANG Yuxiang.Status and Development of Liquid Space Lubricants[J].Lubrication Engineering,2006(6),176-178.
5杨士钊,胡建强,郭力,宗营.合成润滑材料[J].2012,39(1):24-26.YANG Shizhao,HU Jianqiang,GUO Li,ZONG Ying.High-performance Alkylated Naphthalene Base Stocks[J]Synthetic Lubricants,2012,39(1):24-26.
6宋上飞,刘青才,吕升阳.三氟甲磺酸催化萘烷基化研究[J].石油炼制与化工,2018,49(5):71-74.SONG Shangfei,LIU Qingcai,LV Shengyang.Alkylation of naphthalene catalyzed by trifluoromethanesulfonic acid[J].Petroleum Processing and Petrochemicals,2018,49(5):71-74.
7汪廷贵,张乐涛,蔡国星,吾满江·艾力.一种烷基萘基础油的合成及润滑性能研究[J].石油炼制与化工,2013,44(11):96-99.WANG Yangui,ZHANG Letao,CAI Huoxing,Wumanjiang Eli.Study on synthesis of alkyl naphthalene base oils and their lubricating properties,2013,44(11):96-99.
8 Joback K G,Reid R C.Estimation of pure-component properties from group-contributions[J].Chemical Engineering Communications,1987,57(2):233-243.
9 Simon R H M.Estimation of critical properties of organic compounds by the method of group contributions[J].AICHE Journal,1956,2(3):12.
10 Klincewicz K M,Reid R C.Estimation of critical properties with group contribution methods[J].AICHEJournal,1984,30(1):137-142.
11 Lyman Warren J.Handbook of chemical property estimation methods:Environmental behavior of organic compounds[M].American Chemical Society(ACS),Washington,1990.
12 Velzen D V,Cardozo R L,Langenkamp H.A liquid viscosity-temperature-chemical constitution relation for organic compounds[J].Industrial Engineering Chemistry Fundamentals,1972,11(1):20-25.
13 Allan J M,Teja A S.Correlation and prediction of the viscosity of defined and undefined hydrocarbon liquids[J].Canadian Journal of Chemical Engineering,2010,69(4):986-991.
14蔡广庆,张霖宙.烃类液体黏度的定量结构性质预测模型[J].现代化工,2018,38(7):204-207.CAI Guangqing,ZHANG Linzhou.Prediction model of QSPR for hydrocarbon liquid viscosities[J].Modern Chemical Industry,2018,38(7):204-207.
15李诚炜,田松柏,刘泽龙,刘颖荣.直馏减压馏分运动黏度的预测[J].石油学报(石油加工),2009,25(3):452-456.LI Chengwei,TIAN Songbai,LIU Zelong,LIUYingrong.Prediction of kinematic viscosity of vacuumgas oil[J].Acta Petro Lei Sinica(Petroleum Processing Section),2009,25(3):452-456.
16 Box G E,Hunter W G,Hunter J S.Statistics for experimenters:An introduction to design,data analysis,and model building,Wiley series in probability and Mathematical statistics[M].New York:John Wiley&Sons,1978:651-653.
17 Draper N R,Smith H.Applied Regression Analysis[M].Weinheim:Wiley-Interscience,1998:360-429.
18 Friedman J H.Multivariate adaptive regression splines,technical report No.102[D].Stanford:Stanford University,1990.
19汪文虎,秦延龙.烃类物理化学数据手册[M].北京:烃加工出版社,1990:82-436.WANG Wenhu,QIN Yanlong.Handbook for physical and chemical properties of hydrocarbons[M],Beijing:Hydrocarbon Processing Press,1990:82-436.
20 Wiener H.Structural determination of paraffin boiling points[J].Journal of Chemical Physicals,1947,69:17-20.
21 Muller W R.An algorithm for construction of the molecular distance matrix[J].Journal of Computational Chemistry,1987,8:170-173.
22 Stanton D,Jurs P.Development and use of charged partial surface area structural descriptors in computer assisted quantitative structure property relationship studies[J].Analytical Chemistry,1990,62:2323-2329.
23 Bonch E D.Information Theoretic Indices for Characterization of Chemical Structures[M].Chemometrics Series,Vol.5,New York:Research Studies Press Ltd.,1983:1-108.
24 Hall L H,Kier L B.Electrotopological state indices for atom types:A novel combination of electronic,topological and valence state information[J].Journal of Chemical Information and Computer Science,1995,35:1039-1045.
25 Topliss J G,Edwards R P.Chance factors in studies of quantitative structure-activity relationships[J].Journal of Medicinal Chemistry,1979,22:1238-1247.
26 Stah L L,Wold S.Progress of Medical Chemistry,Vol25[M].Amsterdam,Elsevier,1988:12-142.
27寇铨虎.影响烷烃辛烷值高低的结构因素[J].石油学报(石油加工),2010,26(4):556-559.KOU Shuanhu.Factors Affecting Octane Number of Paraffin,2010,26(4):556-559.