运用多谱学分析技术测定高黏聚α烯烃的结构
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摘要
为探究典型的高黏聚α烯烃的精细结构,采用飞行时间质谱、核磁共振波谱和红外光谱方法表征了一种高黏度聚α烯烃(PAO)的结构,确定了该PAO样品主要为聚1-癸烯烃类聚合物,并测定了碳数分布、双键类型以及蒸馏受热后裂解产物的结构信息。质谱结果显示:该PAO聚合度为2~21,其最强峰为五聚1-癸烯;各聚合度PAO几乎都可以检出单烯与链烷烃两类分子。核磁共振氢谱中可见亚乙烯基的同碳偶合烯氢双峰,表明该PAO中存在微量端烯键。经高真空度蒸馏后,蒸馏产物中烯键峰显著增强,表明蒸馏过程产生大量的热裂解产物。红外分析结果表明,PAO样品中的烯键为亚乙烯基双键型,进一步证明了PAO经加氢饱和后残余双键及热解新生成双键皆为端烯类,而非内烯类。
A kind of high viscosity poly alpha-olefin(PAO) as base oil was characterized by time of flight mass spectrometry,and infrared spectrum to investigate the structure of the sample and the fractions after distillation,as well as carbon number distributions and double bond types. The mass spectrometry results show that poly 1-decene with degrees of polymerization of 2—21 is the main component in the PAO sample; the strongest peak is attributed to the pentamer of 1-decene. Both single olefin and alkane can be observed in PAO with different degrees of polymerization. The coupled twin peaks of olefin and hydrogen with the same carbon number as vinylidene are observed by ~1H NMR spectrum,indicating the existence of trace olefin bond at terminal position.The olefin peaks are much stronger after vacuum distillation,demonstrating the occurrence of thermal cracking.The FT-IR indicates that the olefin bound in PAO sample is the vinylidene double bond type,which proves that the remained double bound and newly produced double bound after hydro-saturation of PAO are terminal position double bound,not the internal olefin.
A kind of high viscosity poly alpha-olefin(PAO) as base oil was characterized by time of flight mass spectrometry,and infrared spectrum to investigate the structure of the sample and the fractions after distillation,as well as carbon number distributions and double bond types. The mass spectrometry results show that poly 1-decene with degrees of polymerization of 2—21 is the main component in the PAO sample; the strongest peak is attributed to the pentamer of 1-decene. Both single olefin and alkane can be observed in PAO with different degrees of polymerization. The coupled twin peaks of olefin and hydrogen with the same carbon number as vinylidene are observed by ~1H NMR spectrum,indicating the existence of trace olefin bond at terminal position.The olefin peaks are much stronger after vacuum distillation,demonstrating the occurrence of thermal cracking.The FT-IR indicates that the olefin bound in PAO sample is the vinylidene double bond type,which proves that the remained double bound and newly produced double bound after hydro-saturation of PAO are terminal position double bound,not the internal olefin.
引文
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[2]Buchanan J S,Wu M M,De Caul L.Process for preparing poly alpha olefins and lubricant basestocks from Fischer-Tropsch liquids:The United States,US8440872B2[P].2013-05-14
[3]李红平,冯乐刚,张海忠,等.不同黏度聚α-烯烃合成润滑油基础油的制备[J].石油化工,2013,42(4):384-387
[4]杨晓明,丁洪生,王丽.高黏度指数聚α-烯烃合成润滑油的制备方法[J].工业催化,2012,20(4):40-42
[5]Wang Jing,Zhou Lu,Jiang Wanhe,et al.Tri(4-methoxybenzyloxyl)(pentamethylcyclopentadienyl)titanium/modified MAO catalyzed polymerization of 1-butene[J].China Petroleum Processing and Petrochemical Technology,2014,16(3):69-76
[6]张耀,段庆华,刘依农,等.α-烯烃齐聚制备聚α-烯烃合成油催化剂的研究进展[J].精细石油化工,2011,28(1):82-86
[7]许健,彭立,马国梁,等.合成润滑油基础油茂金属聚α-烯烃合成研究进展[J].现代化工,2012,32(9):28-30,32
[8]Zhu Xinyi,Liu Zelong,Tian Songbai,et al.Analysis of saturates in vacuum residue by solid phase extraction and field desorption time-of-flight mass spectrometry[J].Fuel,2013,112(1):105-110
[9]Hoffmann E D,Stroobant V.Mass Spectrometry[M].3rd Ed.West Sussex:John Wiley&Sons Ltd,2007:31
[10]Niu Luna,Liu Zelong,Tian Songbai.Identification and characterization of sulfur compounds in straight-run diesel using comprehensive two-dimensional GC coupled with TOF MS[J].China Petroleum Processing and Petrochemical Technology,2014,16(3):10-18
[11]Schaub T M,Hendrickson C L,Quinn J P,et al.Instrumentation and method for ultrahigh resolution field desorption ionization Fourier transform ion cyclotron resonance mass spectrometry of nonpolar species[J].Analytical Chemistry,2005,77(5):1317-1324
[12]汪聪慧.高分辨场解吸质谱技术[J].质谱学杂志,1984,5(3):41-53
[13]Feng Yunxia,Chu Xiaoli,Xu Yupeng,et al.Corresponding factors influencing crude oils assay using low-field nuclear magnetic resonance[J].China Petroleum Processing and Petrochemical Technology,2014,16(2):34-39
[14]阳小宇.Ziegler-Natta催化剂催化的1-癸烯齐聚物的结构表征[J].精细化工中间体,2006,36(3):67-69
[15]王宗明,何欣翔,孙殿卿.实用红外光谱学[M].2版.北京:石油工业出版社,1990:218
[16]李春秀,韦夏.红外光谱分析PAO的组成和结构[J].合成润滑材料,2009,36(3):10-13
[17]Li Jingyan,Chu Xiaoli,Tian Songbai.Research on calibration transfer across infrared spectrometric instruments for fast evaluation of crude oils[J].China Petroleum Processing and Petrochemical Technology,2015,17(1):1-5