[1]杜慷慨,郑好英.聚氯甲基苯乙烯的功能化及其在酯化反应中的应用[J].华侨大学学报(自然科学版),2018,39(6):879-884.[doi:10.11830/ISSN.1000-5013.201805020]
　DU Kangkai,ZHENG Haoying.Functionalization of Chloromethyl Polystyrene and Its Application in Esterification[J].Journal of Huaqiao University(Natural Science),2018,39(6):879-884.[doi:10.11830/ISSN.1000-5013.201805020]
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聚氯甲基苯乙烯的功能化及其在酯化反应中的应用()
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《华侨大学学报（自然科学版）》[ISSN:1000-5013/CN:35-1079/N]

卷:
第39卷
期数:
2018年第6期
页码:
879-884
栏目:
出版日期:
2018-11-20

文章信息/Info

Title:
Functionalization of Chloromethyl Polystyrene and Its Application in Esterification
文章编号:
1000-5013(2018)06-0879-06
作者:
杜慷慨;  郑好英
华侨大学 材料科学与工程学院, 福建 厦门 361021
Author(s):
DU Kangkai;  ZHENG Haoying
College of Materials Science and Engineering, Huaqiao University, Xiamen 361021, China
关键词:
聚氯甲基苯乙烯;  功能化;  离子液体;  咪唑;  水杨酸丁酯
Keywords:
chloromethyl polystyrene;  functionalization;  ionic liquids;  imidazole;  n-butyl salicylate
分类号:
TQ426
DOI:
10.11830/ISSN.1000-5013.201805020
文献标志码:
A
摘要:
以聚氯甲基苯乙烯为载体,通过键合法连接磺酸丙基咪唑,制备固载化离子液体［PS-Im+-C3H6SO3H］［p-CH3C6H4SO3-］,并用元素分析、红外光谱(FT-IR)和热重(TG)对其进行表征.以对甲基苯磺酸根为阴离子,将固载化离子液体作为水杨酸丁酯合成的催化剂,通过正交法实验,研究酯化反应的温度、时间、催化剂加入量及醇酸摩尔比反应条件对酯化产率的影响.结果表明:反应温度为120 ℃、反应时间为1.5 h、催化剂用量为反应物质量的6%、醇酸摩尔比为2∶1是合成水杨酸丁酯的最优工艺条件;催化剂重复使用6次后,酯化仍有较高的产率.
Abstract:
The supported ionic liquids ［PS-Im+-C3H6SO3H］［p-CH3C6H4SO3-］ were prepared using chloromethyl polystyrene as supporting material and the propyl sulfosate imidazole bonded on the resin. The products were characterized by elemental analysis, fourier transform infrared spectroscopy(FT-IR)and thermogravimetric analysis(TG). Further, the supported ionic liquids were used as esterification catalyst on n-butyl salicylate with salicylic acid and n-butyl alcohol, using p-methyl phenyl sulfonate as anion. The influence of the reaction temperature, reaction time, the dosage of catalyst, and the initial molar ratio(butanol/salicylic acid)on esterification yield was studied through orthogonal and single factor experiment. The optimum conditions were as follows: the reaction temperature was 120 ℃, the time was 1.5 h, the dosage of catalyst was 6% based on the mass of salicylic acid and n-butyl alcohol, and the molar ratio was 2∶1. In addition, the esterification still had higher yield when the catalyst was reused for 6 times.

参考文献/References:

[1] HOLBREY J D,SEDDON K R.Ionic liquids [J].Clean Products and Processes,1999,1(4):223-236.DOI:10.1007/s100980050036.
[2] BRENNECKE J F,MAGINN E J.Ionic liquids: Innovative fluids for chemical processing [J].AICHE Journal,2001,47(11):2384-2389.DOI:10.1002/aic.690471102.
[3] BONHOTE P,DIAS A P,PAPAGEORGIOU N,et al.Hydrophobic, highly conductive ambient-temperature molten salts[J].Inorganic Chemical,1996,35(5):1168-1178.DOI:10.1021/ic951325x.
[4] KOCH V R,NANJUNDIAH C,APPETECCHI G B,et al.The interracial stability of li with two new solvent-flee ionic liquids: l,2-dimethyl-3-propylimidazolium imide and methide[J].Electrochem Soc,1995,142(7):116-118.DOI:10.1149/1.2044332.
[5] YANG Hongzhou,GU Yanlong,DENG Youquan,et al.Electrochemical activation of carbondioxide in ionic liquid: Synthesis of cyclic carbonates at mild reaction conditions[J].Chemical Communications,2002(3):274-275.DOI:10.1039/B108451H.
[6] SONG C E,ROH E J.Practical method to recycle a chiral(salen)mnepoxidation catalyst by using an ionic liquid [J].Chemical Communications,2000,27(10):837-838.DOI:10.1039/B001403F.
[7] KIM K S,DEMBERELNYAMBA D,LEE H.Size-selective synthesis of gold and platinum nanoparticles using novel thiol-functionalized ionic liquids [J].Langmuir,2004,20(3):556-560.DOI:10.1021/la0355848.
[8] WASSERSCHEID P,GOEDON C M,HILGERS C,et al.Ionic liquids: Polar, but weakly coordinating solvents for the first biphasic oligomerisation of ethene to higher-olefins with cationic Ni complexes[J].Chem Commun,2001(13):1186-1187.DOI:10.1039/B101400P.
[9] TANG Long,DING Li,CHANG Weixing,et al.SnCl2-mediated carbonyl allylation of aldehydes and ketones in ionic liquid[J].Tetrahedron Letters,2006,47(3):303-306.DOI:10.1016/j.tetlet.2005.11.022.
[10] 郝苏霞,王桂荣,栾艳勤,等.离子液体在Friedel-Crafts反应中应用进展[J].化工进展,2009,28(6):953-957.DOI:10.16085/j.issn.1000-6613.2009.06.001.
[11] 赵强,林金清.磺酸基功能化季铵盐离子液体催化油酸制备生物柴油[J].华侨大学学报(自然科学版),2013,34(6):662-666.DOI:10.11830/ISSN.1000-5013.2013.06.0662.
[12] 刘晔,李敏,路勇,等.功能离子液体复合体系中钯催化的Heck偶联反应[J].高等学校化学学报, 2007, 28(4):723-726.DOI:10.3321/j.issn:0251-0790.2007.04.02.3.
[13] 孙晓杰、邢钧、翟毓秀,等.离子液体在气相色谱固定相中的应用[J].化学进展,2014,26(4):647-656.DOI:10.7536/PC130847.
[14] CHRISTIAN P,MEHNERT D.Supported ionic liquid phases[J].Chemistry European Journal,2005,11(1):50-56.DOI:10.1002/chem.200400683.
[15] LI Dongmei,SHI Feng,GUO Shu,et al.One-pot synthesis of silica gel confined functional ionic liquids: Effective catalysts for deoximation under mild conditions[J].Tetrahedron Lett,2004,45(2):265-268.DOI:10.1002/chin.200415062.
[16] 崔露丹,马磊.功能化活性炭固载离子液体催化剂[J].浙江化工,2012,43(10):12-15.DOI:10.3969/j.issn.1006-4184.2012.10.004.
[17] 孙亚飞,林金清,左霜,等.功能化季铵盐离子液体在制备生物柴油中的应用[J].华侨大学学报(自然科学版),2011,32(6):657-662.DOI:10.11830/ISSN.1000-5013.2011.06.0657.
[18] 曹渊,文毅,徐彦琴,等.介孔分子筛固载离子液体及其在催化有机反应中的应用[J].化学通报,2012,75(10):879-885.DOI:10.14159/j.cnki.0441-3776.2012.10.010.
[19] 汤小芳,冯雷,祁贵国.硅胶固载[HSO3-Pmim]HSO4催化合成对羟基苯甲酸乙酯[J].日用化学工业,2013,43(6):441-444.DOI:10.13218/j.cnki.csdc.2013.06.008.
[20] 余加祐,王明章,张秀玲,等.固载化离子液体在催化加氢反应中的研究进展[J].大连工业大学学报,2008,27(2):123-128.DOI:10.19670/j.cnki.dlgydxxb.2008.02.008.
[21] 郑好英,杜慷慨.氯球固载化离子液体的制备及其在乙酸异戊酯合成中的应用[J].华侨大学学报(自然科学版),2017,38(6):824-829.DOI:10.11830/ISSN.1000-5013.2016.06089.
[22] ZHANG Qiang,LUO Jun,WEI Yunyang.A silica gel supported dual acidic ionic liquid: An efficient and recyclable heterogeneous catalyst for the one-pot synthesis of amidoalkyl naphthols[J].Green Chemistry,2010,12(12):2246-2254.DOI:10.1039/C0GC00472C.
[23] XU Zhenjin,WAN Hui,MIAO Jinmei,et al.Reusable and efficient polystyrene-supported acidic ionic liquid catalyst for esterifications[J].Journal of Molecular Catalysis A Chemical,2010,332(1/2):152-157.DOI:10.1016/j.molcata.2010.09.011.
[24] MIAO Jinmei,WAN Hui,SHAO Yanbing,et al.Acetalization of carbonyl compounds catalyzed by acidic ionic liquid immobilized on silica gel[J].Journal of Molecular Catalysis A Chemical,2011,348(1/2):77-82.DOI:10.1016/j.molcata.2011.08.005.
[25] FIRDOVSI S T,YAGOUB M,PARVIN A E.Transesterification reaction of dimethyl terephthalate by 2-ethylhexanol in the presence of heterogeneous catalysts under solvent-free condition[J].Chinese Journal of Chemistry,2007,25(2):246-249.DOI:10.1002/cjoc.200790049.
[26] 孟启,戎志峰,肖网琴,等.Cyclen型聚苯乙烯树脂的结构与吸附性能[J].合成树脂及塑料,2014,31(4):13-16.DOI:10.3969/j.issn.1002-1396.2014.04.005.
[27] JIANG Yingying,WU Youting,WANG Wenting,et al.Permeability and selectivity of sulfur dioxide and carbon dioxide in supported ionic liquid membranes[J].Chinese Journal of Chemical Engineering,2009,17(4):594-601.DOI:10.1016/S1004-9541(08)60249-9.
[28] 魏作君,李艳,李斐瑾,等.固定化Brönsted酸性离子液体催化酯化反应[J].化工学报,2009,60(6):1452-1458.DOI:10.3321/j.issn:0438-1157.2009.06.018.
[29] MIAO Jinmei,WAN Hui,GUAN Guofeng.Synthesis of immobilized Brnsted acidic ionic liquid on silica gel as heterogeneous catalyst for esterification[J].Catalysis Communications,2011,12(5):353-356.DOI:10.1016/j.catcom.2010.10.014.
[30] 杨雨林,肖明,王跃川.SO3H-功能化离子液体的合成及用于催化酯化反应的研究[J].化学研究与应用,2013,25(7):1055-1059.DOI:10.3969/j.issn.1004-1656.2013.07.026.
[31] YANG Jinbei,ZHOU Lihua,GUO Xiaoting,et al.Study on the esterification for ethylene glycol diacetate using supported ionic liquids as catalyst: Catalysts preparation, characterization, and reaction kinetics, process[J].Chemical Engineering Journal,2015,280:147-157.DOI:10.1016/j.cej.2015.05.096.

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备注/Memo

备注/Memo:
收稿日期: 2018-05-29
通信作者: 杜慷慨(1963-),男,副教授,博士,主要从事高分子材料改性及有机合成的研究.E-mail:dukang@hqu.edu.cn.
基金项目: 国家自然科学基金资助项目(21246008); 福建省自然科学基金资助项目(2016J01060)
更新日期/Last Update: 2018-11-20