润滑油硫化烷基酚钙清净分散剂组成研究
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摘要
清净剂在润滑油添加剂中所占比例将近一半,应用极为广泛。其组成对润滑油性能有很大的影响,不同厂家甚至不同批次的产品在分水和抗水洗性能上都会存在差异,因而对此类添加剂的结构和组成进行研究是十分必要的,这对其生产、合成和使用有着指导作用。
本文以国外清净剂S206Ⅰ及国内生产的两个批次润滑油清净剂(S206Ⅱ和S206Ⅲ)为样本,着重剖析了这几个典型硫化烷基酚钙的组成、结构,并研究了不同组分对分水性和抗水洗性能的影响。本文采用动态薄膜渗析法,提取了有效成分。利用色谱、核磁共振质谱等手段比较了三者在结构组成上的差别,并考察了分水性能影响因素。
研究表明国外型号S206Ⅰ的产品无论是从有效含量和分子量上看,都比国内两个产品高,并且具有分散度较小的优点。从组成上研究,国外样品S206Ⅰ在产品合成中残余的游离烷基酚含量最小,性能最差的样品S206Ⅱ则游离烷基酚残余含量最高；国内产品中含有脂肪酸等物质,特别是其中性能较次的样品S206Ⅲ中,还含有胺类物质等杂质。从结构上研究,国内外钙盐样品都为对位取代,但国外样品烷基链的支化度较大,而国内S206Ⅲ支化度最小。研究还发现,样品合成中作为助剂而少量残余的脂肪酸,会使分水性能变差,乳化层增加；样品中存在少量脂肪胺,虽可提高碱值,但会造成添加剂有效组成(碱性部分)在水中稳定性变差。两者对润滑油分水和抗水洗性能都不利。
High-alkaline detergent is applied widely in lubricant additives. It is quiet different in water separation and washing resistance among productions from different companies or batches even in the same company, which has a great impact on lubricant performance.
For guiding the production, synthesis and use of the product, this paper analyses the differences in compositions and structures of three typical sulfurized calcium alkyl phenolates which are used as detergents in lubricate base oil. In addition, the effect factors of water separation and washing resistance from different compositions is also studied. The effective components are extracted by rubber membrane dialysis. The differences in the structures and compositions of three detergents have been compared on the basis of elemental analyses, infrared spectroscopy (IR), and nuclear magnetic resonance (NMR), etc.
The results show that the detergent with excellent performance, S206Ⅰhas the greatest advantage of effective content among these three detergents. Besides, its average molecular weight is the largest and its dispersion degree is the smallest. From the composition, S206Ⅰcontains the least free alkylphenol remained in the synthesis, S206Ⅱa little more, S206Ⅲthe most. In addition, several compositions such as stearic acid can be found in S206. And S206Ⅱ, performance inferior sample in S206, contains most impurities such as amine compounds. From the structure, all the samples are para-sulfurized alkyl phenolate. But the long alkyl branching degree in S206Ⅰis the greatest, then S206Ⅱ, the smallest is in S206Ⅲ. The study also finds that stearic acid remained in samples can lead to poor water-dividing performance and increasing the emulsification layer. Meanwhile, amine compound will decrease additive's stability in water although it can enhance additive's total based number.
本文以国外清净剂S206Ⅰ及国内生产的两个批次润滑油清净剂(S206Ⅱ和S206Ⅲ)为样本,着重剖析了这几个典型硫化烷基酚钙的组成、结构,并研究了不同组分对分水性和抗水洗性能的影响。本文采用动态薄膜渗析法,提取了有效成分。利用色谱、核磁共振质谱等手段比较了三者在结构组成上的差别,并考察了分水性能影响因素。
研究表明国外型号S206Ⅰ的产品无论是从有效含量和分子量上看,都比国内两个产品高,并且具有分散度较小的优点。从组成上研究,国外样品S206Ⅰ在产品合成中残余的游离烷基酚含量最小,性能最差的样品S206Ⅱ则游离烷基酚残余含量最高；国内产品中含有脂肪酸等物质,特别是其中性能较次的样品S206Ⅲ中,还含有胺类物质等杂质。从结构上研究,国内外钙盐样品都为对位取代,但国外样品烷基链的支化度较大,而国内S206Ⅲ支化度最小。研究还发现,样品合成中作为助剂而少量残余的脂肪酸,会使分水性能变差,乳化层增加；样品中存在少量脂肪胺,虽可提高碱值,但会造成添加剂有效组成(碱性部分)在水中稳定性变差。两者对润滑油分水和抗水洗性能都不利。
High-alkaline detergent is applied widely in lubricant additives. It is quiet different in water separation and washing resistance among productions from different companies or batches even in the same company, which has a great impact on lubricant performance.
For guiding the production, synthesis and use of the product, this paper analyses the differences in compositions and structures of three typical sulfurized calcium alkyl phenolates which are used as detergents in lubricate base oil. In addition, the effect factors of water separation and washing resistance from different compositions is also studied. The effective components are extracted by rubber membrane dialysis. The differences in the structures and compositions of three detergents have been compared on the basis of elemental analyses, infrared spectroscopy (IR), and nuclear magnetic resonance (NMR), etc.
The results show that the detergent with excellent performance, S206Ⅰhas the greatest advantage of effective content among these three detergents. Besides, its average molecular weight is the largest and its dispersion degree is the smallest. From the composition, S206Ⅰcontains the least free alkylphenol remained in the synthesis, S206Ⅱa little more, S206Ⅲthe most. In addition, several compositions such as stearic acid can be found in S206. And S206Ⅱ, performance inferior sample in S206, contains most impurities such as amine compounds. From the structure, all the samples are para-sulfurized alkyl phenolate. But the long alkyl branching degree in S206Ⅰis the greatest, then S206Ⅱ, the smallest is in S206Ⅲ. The study also finds that stearic acid remained in samples can lead to poor water-dividing performance and increasing the emulsification layer. Meanwhile, amine compound will decrease additive's stability in water although it can enhance additive's total based number.
引文
[1]赵国玺,朱砂瑶.表面活性剂作用原理[M].北京：中国轻工业出版社.2003：50-272.
[2]付喜胜,姚文钊,张龙华等.润滑油添加剂的现状及发展趋势.汽车工艺与材料.2005,5：1-6.
[3]袁大辉,戴凤阁,赵殿富.润滑油添加剂的种类与开发[J].河南化工.2002,(8)：7-9
[4]刘文军,徐延齐,姜立军.国内外润滑油添加剂市场概况及发展[J].齐鲁化工.专论与综述.2004,32(2)：112-114
[5]王桂琴.高碱值硫化烷基酚钙的研制.润滑油[J].2003,18(5)：49-52
[6]堀敬,上田早苗.石油技术(日).1990,13(8)：38-40
[7]堀敬,上田早苗.石油学会志(日).1991,34(5)：1-6
[8]堀敬,上田早苗.日本化工会志(日).1991,(12)：446-51
[9]堀敬,上田早苗.石油学会志(日).1991,34(5)：1-6
[10]Heldeweg,rudolf,frank etc.(SHELL) EP.168(110)
[11]张霖霖,周勇强,谢浩东.紫外分光光度法直接测定废水中微量油的研究[J].光谱与光谱分析.2001,21(5)：716-718
[12]王秀君,郑连义,戴俊台.双波长紫外光谱法快速测定溶解油中单环及双环芳烃含量[J].河北化工.2002,(3)：43-44
[13]王雷,杨新建,寇欣.紫外分光光度计在中药分析中的应用进展[J].天津要学.2003
[14]祝玉杰,李剑群,王焕梅,陈立仁,付兴国.润滑油金属清净分散剂的质谱研究[J].润滑油.2003,18(5)：53-56
[15]藤田稔.JETI[J].1991.39(13)：28-34
[16]成跃祖.精细石油化工[J].fuel.1986,(3)：45-54
[17]成跃祖.色谱[J].1985,2(5)：268-272
[18]李占群,孔素玲,左伟,宋茂森.硫化烷基酚钙添加剂的组成分分析及结构[J].石油化工.1998,27：834-837
[19]宋茂森,李占群,孔素玲.硫化烷基酚钙型添加剂的化学结构研究[J].兰州大学学报(自然科学版).1991,27(4)：98-103
[20]左伟,宋茂森,余晓红.高效液相色谱用于硫化烷基酚钙添加剂水解产物的分离制备[J].色谱.1990,8(3)：197-198
[21]ASTM D 2896-85
[22]Said E.Z..Infrared spectrophotometric Determination of the Alkylinity of Overbased Pe-troleum Sulphonates[J].Analyst.1987,112(4):499-500
[23]Kurt J.Irgolic, Jon E.Hobill. Simultaneous Inductively Coupled argon Plasma Atomic Emission Spectrometrer as a Sulful specific Dectector for the HPLC Analysis of Sulfulcon-taining Surfactants[J]. Spectrochimica Acta.1987,(1):269-273
[24]J.D.kaight and R.House.JAOCS.1959,36:195-200
[25]Atson Nakae, etal.Determination of Alkhl chain Distribution of Alkylbenzene sulfonates by Liquid Chroatograh,Anal.Chem.1981, (53):1818-1821
[26]H.R.Menaz, C.L. Porec.Determination of Alkhl chain Distribution in lubricating Oil additives of the type alkyl Aryl Sulfonate by HPLC.J.High.Result[J].Chromatogr.1989,12(8): 562-256
[27]苏克曼.润滑油清净分散剂-石油磺酸盐的分析[J].华东化工学院学报.1993,19(6)：754-758
[28]鲁静,苏克曼,严正泽等.石油磺酸盐类清净分散剂的组成和结构分析[J].润滑油.1996,11(3)：44-48
[29]宋宪芝,张有序,李向榕.新型无灰分散剂的结构分析研究[J].石油炼制与化工.1998,29(6)：62-66
[30]J P.Coates.The analysis of lubricating oils and oil additives by Thin-layer chromatogra-phy[J]. Jounal of Institute of petroleum.1971,57(7):556
[31]Amos R.Edgar, Albaugh W.Chromatography in petroleum analysis[J].1988,8(2):39-44
[32]Colyer C C, Gergel W C.Chemistry and technology of Lubricants [J].1992
[33]付兴国.国内外硫化烷基酚盐化学组成结构的对比研究.1990
[34]付兴国,张景河等.国内外硫化烷基酚盐组成结构分析研究[J].石油炼制与化工1995,26(1)：33-36
[35]林洪安.内燃机油混对试验的研究[J].润滑油.1990,(4)：33-36
[36]曾大贵等.含不同添加剂内燃机油混存混用研究[J].石油商技.1992,(4)：8-12
[37]朱九峰等.柴油机油混溶性的研究[J].石油商技.1994,(1)：21-23
[38]蒋明俊,郭小川,董浚修.内燃机油添加剂之间的相互作用的研究[J].润滑油.1998,13(6)：47-50
[39]王莉萍.船用润滑油系列知识之一[J].润滑油.2000,15(5)：51-60.
[40]魏海军,马玉莉,王宏志等.船用润滑油的使用与管理[M].大连：大连海事学院出版社.2006：1-29.
[41]魏海军,孙培廷.船用润滑油的选用[J].世界海运.2003,26(3)：53-54.
[42]王平.船用润滑油技术工作展望[J].石油商机.2008,6：12-13.
[43]柴隽.润滑油技术发展展望[J].合成润滑材料.2007,34(4)：13-15
[44]颜皓,张法智,梁海萍,侯滨.水对高碱值硫化烷基酚钙清净剂使用性能的影响[J].石油炼制与化工.2007,38(6)：52-54
[45]范金凤,乔庆文.硫化烷基酚钙分水性能的影响因素探讨[J].石油商技.2010,28(1)：26-27
[46]段连春.高碱值硫化烷基酚钙的合成研究[J].辽宁化工.2000,29(4)：256-259
[47]姚文钊,付兴国,梁李群芳.烷基水杨酸盐的胶体结构与其稳定性关系研究[J].润滑油.2001,16(2)：55-59
[48]平海宏,李宝城,张晓岩.石油化工分析[M].化学工业出版社.2005.5,第一版：88-133
[49]朱淮武.有机分子结构波谱分析[M].化学工业出版社.2005.9,第一版：29-158
[50]Sadiler Research laboratories.Sadiler Standard C-NMR Spectra.vol 1-4117C,332C, 488C, vol 5-8 1229c,vol9-121754C,vol25-48 4900,4985c
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[2]付喜胜,姚文钊,张龙华等.润滑油添加剂的现状及发展趋势.汽车工艺与材料.2005,5：1-6.
[3]袁大辉,戴凤阁,赵殿富.润滑油添加剂的种类与开发[J].河南化工.2002,(8)：7-9
[4]刘文军,徐延齐,姜立军.国内外润滑油添加剂市场概况及发展[J].齐鲁化工.专论与综述.2004,32(2)：112-114
[5]王桂琴.高碱值硫化烷基酚钙的研制.润滑油[J].2003,18(5)：49-52
[6]堀敬,上田早苗.石油技术(日).1990,13(8)：38-40
[7]堀敬,上田早苗.石油学会志(日).1991,34(5)：1-6
[8]堀敬,上田早苗.日本化工会志(日).1991,(12)：446-51
[9]堀敬,上田早苗.石油学会志(日).1991,34(5)：1-6
[10]Heldeweg,rudolf,frank etc.(SHELL) EP.168(110)
[11]张霖霖,周勇强,谢浩东.紫外分光光度法直接测定废水中微量油的研究[J].光谱与光谱分析.2001,21(5)：716-718
[12]王秀君,郑连义,戴俊台.双波长紫外光谱法快速测定溶解油中单环及双环芳烃含量[J].河北化工.2002,(3)：43-44
[13]王雷,杨新建,寇欣.紫外分光光度计在中药分析中的应用进展[J].天津要学.2003
[14]祝玉杰,李剑群,王焕梅,陈立仁,付兴国.润滑油金属清净分散剂的质谱研究[J].润滑油.2003,18(5)：53-56
[15]藤田稔.JETI[J].1991.39(13)：28-34
[16]成跃祖.精细石油化工[J].fuel.1986,(3)：45-54
[17]成跃祖.色谱[J].1985,2(5)：268-272
[18]李占群,孔素玲,左伟,宋茂森.硫化烷基酚钙添加剂的组成分分析及结构[J].石油化工.1998,27：834-837
[19]宋茂森,李占群,孔素玲.硫化烷基酚钙型添加剂的化学结构研究[J].兰州大学学报(自然科学版).1991,27(4)：98-103
[20]左伟,宋茂森,余晓红.高效液相色谱用于硫化烷基酚钙添加剂水解产物的分离制备[J].色谱.1990,8(3)：197-198
[21]ASTM D 2896-85
[22]Said E.Z..Infrared spectrophotometric Determination of the Alkylinity of Overbased Pe-troleum Sulphonates[J].Analyst.1987,112(4):499-500
[23]Kurt J.Irgolic, Jon E.Hobill. Simultaneous Inductively Coupled argon Plasma Atomic Emission Spectrometrer as a Sulful specific Dectector for the HPLC Analysis of Sulfulcon-taining Surfactants[J]. Spectrochimica Acta.1987,(1):269-273
[24]J.D.kaight and R.House.JAOCS.1959,36:195-200
[25]Atson Nakae, etal.Determination of Alkhl chain Distribution of Alkylbenzene sulfonates by Liquid Chroatograh,Anal.Chem.1981, (53):1818-1821
[26]H.R.Menaz, C.L. Porec.Determination of Alkhl chain Distribution in lubricating Oil additives of the type alkyl Aryl Sulfonate by HPLC.J.High.Result[J].Chromatogr.1989,12(8): 562-256
[27]苏克曼.润滑油清净分散剂-石油磺酸盐的分析[J].华东化工学院学报.1993,19(6)：754-758
[28]鲁静,苏克曼,严正泽等.石油磺酸盐类清净分散剂的组成和结构分析[J].润滑油.1996,11(3)：44-48
[29]宋宪芝,张有序,李向榕.新型无灰分散剂的结构分析研究[J].石油炼制与化工.1998,29(6)：62-66
[30]J P.Coates.The analysis of lubricating oils and oil additives by Thin-layer chromatogra-phy[J]. Jounal of Institute of petroleum.1971,57(7):556
[31]Amos R.Edgar, Albaugh W.Chromatography in petroleum analysis[J].1988,8(2):39-44
[32]Colyer C C, Gergel W C.Chemistry and technology of Lubricants [J].1992
[33]付兴国.国内外硫化烷基酚盐化学组成结构的对比研究.1990
[34]付兴国,张景河等.国内外硫化烷基酚盐组成结构分析研究[J].石油炼制与化工1995,26(1)：33-36
[35]林洪安.内燃机油混对试验的研究[J].润滑油.1990,(4)：33-36
[36]曾大贵等.含不同添加剂内燃机油混存混用研究[J].石油商技.1992,(4)：8-12
[37]朱九峰等.柴油机油混溶性的研究[J].石油商技.1994,(1)：21-23
[38]蒋明俊,郭小川,董浚修.内燃机油添加剂之间的相互作用的研究[J].润滑油.1998,13(6)：47-50
[39]王莉萍.船用润滑油系列知识之一[J].润滑油.2000,15(5)：51-60.
[40]魏海军,马玉莉,王宏志等.船用润滑油的使用与管理[M].大连：大连海事学院出版社.2006：1-29.
[41]魏海军,孙培廷.船用润滑油的选用[J].世界海运.2003,26(3)：53-54.
[42]王平.船用润滑油技术工作展望[J].石油商机.2008,6：12-13.
[43]柴隽.润滑油技术发展展望[J].合成润滑材料.2007,34(4)：13-15
[44]颜皓,张法智,梁海萍,侯滨.水对高碱值硫化烷基酚钙清净剂使用性能的影响[J].石油炼制与化工.2007,38(6)：52-54
[45]范金凤,乔庆文.硫化烷基酚钙分水性能的影响因素探讨[J].石油商技.2010,28(1)：26-27
[46]段连春.高碱值硫化烷基酚钙的合成研究[J].辽宁化工.2000,29(4)：256-259
[47]姚文钊,付兴国,梁李群芳.烷基水杨酸盐的胶体结构与其稳定性关系研究[J].润滑油.2001,16(2)：55-59
[48]平海宏,李宝城,张晓岩.石油化工分析[M].化学工业出版社.2005.5,第一版：88-133
[49]朱淮武.有机分子结构波谱分析[M].化学工业出版社.2005.9,第一版：29-158
[50]Sadiler Research laboratories.Sadiler Standard C-NMR Spectra.vol 1-4117C,332C, 488C, vol 5-8 1229c,vol9-121754C,vol25-48 4900,4985c
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