丁醇与BF_3络合物结构及其催化1-癸烯聚合性能
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摘要
BF_3与正丁醇络合物在催化1-癸烯聚合的过程中具有重要的作用,BF_3·正丁醇络合物结构随BF_3在正丁醇中质量分数的不同而不同。以BF_3与正丁醇为原料合成了含有不同w(BF_3)的BF_3·正丁醇络合物。采用~1H NMR、IR与~(19)F NMR对不同w(BF_3)的BF_3·正丁醇络合物的结构进行表征。并对不同w(BF_3)的BF_3·正丁醇络合物的催化1-癸烯的聚合性能进行研究。结果表明,当w(BF_3)=5%～33%,络合物主要是BF_3·(n-BuOH)_2,且其质量分数为9%～89%;w(BF_3)>33%,络合物中产生BF_3·n-BuOH,且w (BF_3·nBuOH)随着w (BF_3)的增加而增加,w (BF_3)=45%,w(BF_3·n-BuOH)=92%。然而w(BF_3)=5%～33%,络合物无催化活性。w(BF_3)=45%,其1-癸烯聚合转化率为27.32%,且选择性为11.13%(二聚体)、12.08%(三聚体)与4.11%(四聚体),并确定了BF_3·正丁醇络合物中催化1-癸烯聚合的有效催化结构为BF_3·n-BuOH,该研究结果为以BF_3·正丁醇络合物为催化剂,催化1-癸烯聚合合成聚α-烯烃(PAO)工业提供理论指导,为可控工艺提供技术支持。
The complexes of BF_3 with n-Butanol(n-BuOH)played an important role in catalyzing n-decene polymerization.The structures of BF_3·n-BuOH complexes were varied with the mass fraction of BF_3 in n-Butanol.In this paper,~1H NMR,IR and ~(19)F NMR were employed to characterize the structures of BF_3 complexes.The catalytic performance of BF_3·n-BuOH complexes for n-decene polymerization was also studied.The result showed that BF_3·(n-BuOH)_2 was the main structure when the mass fraction of BF_3 was 5%～33% and the content of BF_3·(n-BuOH)_2 was 9%～89%.Meanwhile,the content of BF_3·n-BuOH was increased with the increase of mass fraction of BF_3,and the content of BF_3·n-BuOH was 92% when the mass fraction of BF_3 was over 45%.However,there was no catalytic activity for BF_3·n-BuOH complexes when mass fraction of BF_3 was 5%～33%.When the mass fraction of BF_3 was 45%,the conversion of n-decene polymerization was 27.32%and the selectivity of product were 11.13%(dimer),12.08%(trimer)and 4.11%(tetramer).And the effective catalytic structure for the n-decene polymerization by BF_3·n-BuOH complexes was determined to be BF_3·n-BuOH.The results of this study provided theoretical guidance for the synthesis of PAO industry by using BF_3·n-BuOH to catalyze n-decene polymerization and technical support for controllable processes.
The complexes of BF_3 with n-Butanol(n-BuOH)played an important role in catalyzing n-decene polymerization.The structures of BF_3·n-BuOH complexes were varied with the mass fraction of BF_3 in n-Butanol.In this paper,~1H NMR,IR and ~(19)F NMR were employed to characterize the structures of BF_3 complexes.The catalytic performance of BF_3·n-BuOH complexes for n-decene polymerization was also studied.The result showed that BF_3·(n-BuOH)_2 was the main structure when the mass fraction of BF_3 was 5%～33% and the content of BF_3·(n-BuOH)_2 was 9%～89%.Meanwhile,the content of BF_3·n-BuOH was increased with the increase of mass fraction of BF_3,and the content of BF_3·n-BuOH was 92% when the mass fraction of BF_3 was over 45%.However,there was no catalytic activity for BF_3·n-BuOH complexes when mass fraction of BF_3 was 5%～33%.When the mass fraction of BF_3 was 45%,the conversion of n-decene polymerization was 27.32%and the selectivity of product were 11.13%(dimer),12.08%(trimer)and 4.11%(tetramer).And the effective catalytic structure for the n-decene polymerization by BF_3·n-BuOH complexes was determined to be BF_3·n-BuOH.The results of this study provided theoretical guidance for the synthesis of PAO industry by using BF_3·n-BuOH to catalyze n-decene polymerization and technical support for controllable processes.
引文
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[5]徐婷婷,孙维,马立莉,等.烯烃聚合茂金属催化剂研究进展[J].精细石油化工进展,2017,18(5):33-35.
[6]DE KLERK A.Oligomerization of 1-hexene and 1-octene over solid acid catalysts[J].I&EC Res,2005,44(11):3887-3893.
[7]WANG S H,WANG L B,LIU T,et al.Characterization and apparent kinetics of polymerization of 1-decene catalyzed by boron trifluoride/alcohol system[J].China Pet and Process Pe,2017,19(3):16-22.
[8]SHUBKIN RL.Synthetic lubricants by oligomerization and hydrogenation:US3780128[P].1973-12-18.
[9]SCHEUERMANN S S,EIBL S,BARTL P.Detailed characterization of isomers present in poly alpha olefin dimer and the effect of isomeric distribution on bulk properties[J].Lubr Sci,2011,23(5):221-232.
[10]MOORE L D,FELS D R,SEAY A B,et al.PAO-based synthetic lubricants in industrial applications[J].Tribol Lubr Technol,2003,59(1):23-30.
[11]李君良,吴亚荣.1-癸烯的生产技术及应用[J].石化技术,2008,15(1):66-68.
[12]江玲.1-癸烯齐聚物润滑油基础油的合成研究[D].上海:华东理工大学,2011.
[13]张志峰,丁洪生,权成光,等.癸烯-1聚α-烯烃合成油的合成及性质[J].辽宁石油化工大学学报,2005,25(3):24-27.
[14]王斯晗,王力博,刘通,等.BF3催化混合C10烯烃制备α-烯烃润滑油基础油[J].化学反应工程与工艺,2016,32(6):528-535.
[15]常建华,董绮功.波谱原理及解析[M].北京:科学出版社,2012:131.
[16]AKITT J W.NMR and chemistry,an introduction to modern NMR spectroscopy,3rd ed[M].London:Chapman&Hall,1992:135-162.
[17]DEROUAULT J,DZIEMBOWSKA T,FOREL M T.Infrared and Raman investigation of the liquid addition compounds BF3-CH3OH and BF3-2CH3OH[J].J Mol Struct,1978(47):59-63.