侧链PEG基聚合物的制备及其催化酯化反应性能
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摘要
聚乙二醇单(乙烯基苄基)醚(PEG-VBE)和聚乙二醇二(乙烯基苄基)醚(PEG-DVBE)是重要的可聚合聚乙二醇衍生物,可用于催化剂载体及功能高分子的合成。本文以氢氧化钾为碱,乙烯基苄基氯(VBC)与乙二醇、一缩二乙二醇、二缩三乙二醇、PEG400、PEG600和PEG1500反应,高效合成了一系列乙烯基苄基聚乙二醇衍生物,乙烯基苄基氯的转化率可达96%以上,PEG-VBE的分离收率为32%～93%。乙烯基衍生物在过硫酸钾引发下聚合得到水溶性高分子,产物经1H NMR、ESI-HRMS及FT-IR分析表征。以制备的水溶性PEG基聚合物为微反应器,研究了苯甲酸与甲醇的酯化反应,在优化的条件下,苯甲酸的转化率可达99%以上,催化体系循环5次后,催化活性几乎没有下降。
Polyethylene glycol vinylbenzyl ether(PEG-VBE) and polyethylene glycol di(vinylbenzyl) ether(PEG-DVBE) are important polymerizable PEG-derivatives,which have good applications in the fields of catalyst support and functional polymers.In this paper,a series of PEG-VBE and PEG-DVBE were prepared by reaction of vinyl benzyl chloride(VBC) with ethylene glycol,diethylene glycol,triethylene glycol,PEG400,PEG600,and PEG1500 using KOH as base.The conversion rate of VBC is more than 96%,and the separation yield of PEG-VBE is in range of 32% ～ 93%.The products were characterized by1 H NMR、ESI-HRMS and FT-IR.Using PEG based polymer as microreactor,the esterification of benzoic acid and methanol was investigated.The combination of PEG based polymer with sulfuric acid has very good catalytic activity on the esterification.At the optimized condition,the conversion of benzoic acid is up to 99%.The catalytic activity is barely decreased after five cycles.
Polyethylene glycol vinylbenzyl ether(PEG-VBE) and polyethylene glycol di(vinylbenzyl) ether(PEG-DVBE) are important polymerizable PEG-derivatives,which have good applications in the fields of catalyst support and functional polymers.In this paper,a series of PEG-VBE and PEG-DVBE were prepared by reaction of vinyl benzyl chloride(VBC) with ethylene glycol,diethylene glycol,triethylene glycol,PEG400,PEG600,and PEG1500 using KOH as base.The conversion rate of VBC is more than 96%,and the separation yield of PEG-VBE is in range of 32% ～ 93%.The products were characterized by1 H NMR、ESI-HRMS and FT-IR.Using PEG based polymer as microreactor,the esterification of benzoic acid and methanol was investigated.The combination of PEG based polymer with sulfuric acid has very good catalytic activity on the esterification.At the optimized condition,the conversion of benzoic acid is up to 99%.The catalytic activity is barely decreased after five cycles.
引文
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[3]Y C Han,Y Chu.J.Mol.Catal.A,2005,237(1-2):232~237.
[4]Y Zheng,Y Zheng,S Yang et al.Green Chem.Lett.Rev.,2017,10(4):202~209.
[5]赵地顺,刘猛帅,徐智策等.化工进展,2011,30(11):2287~2323.
[6]H D Shin,J H Kim,T K Kim et al.Enzyme.Microb.Tech.,2002,2002(30):835~842.
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[9]王鹏,张静丽,卿光焱.材料导报,2015,29(5):1~19.
[10]D M Vriezema,M C Aragones,J.Elemans et al.Chem.Rev.,2005,105(4):1445~1489.
[11]Y Zhu,B Yang,S Chen et al.Prog.Polym.Sci.,2017,64:1~22.
[12]R Akiyama,S Kobayashi.Chem.Rev.,2009,109(2):594~642.
[13]J Soule,H Miyamura,S Kobayashi.J.Am.Chem.Soc.,2011,133(46):18550~18553.
[14]T Yasukawa,H Miyamura,S Kobayashi.J.Am.Chem.Soc.,2012,134(41):16963~16966.
[15]K Kamahori,K Ito,S Itsuno.J.Org.Chem.,1996,61(23):8321~8324.
[16]M Renil,M Meidal.Tetrahed.Lett.,1996,37(34):6185~6188.
[17]M Wilson,K Paech,W Zhou et al.J.Org.Chem.,1998,63(15):5094~5099.
[18]F Hua,W Yuan,P Britt et al.Soft Matter,2013,9(37):8897~8903.
[19]C Mugemana,B Chen,K Bukhryakov et al.Chem.Commun.,2014,50(58):7862~7865.
[20]Y Jia,L Liu,B Lei et al.Macromolecules,2011,44(16):6311~6317.
[21]S Feng,Q Wang,Y Gao et al.J.Appl.Polym.Sci.,2009,114(4):2071~2078.
[22]Y Pérez,C Aprile,A Corma et al.Catal.Lett.,2009,134(3/4):204~209.
[23]S Lee,K Yoon,M Song et al.Chem.Mater.,2011,24(1):115~122.
[24]T Kuo,L Chien,Y Chang et al.RSC Adv.,2014,4(87):47066~47075.
[25]赵会晶,朱煜,赵文等.化学通报,2015,78(2):182~185.
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[27]G Liu,X Wang,F Zhou et al.Appl.Mater.Interf.,2013,5(21):10842~10852.