作者：张冷思¹, 柴文², 吉海玲², 李静²

作者单位：1. 常州大学石油化工学院, 江苏 常州 213164;
2. 常熟理工学院化学与材料工程学院, 江苏 常熟 215500

关键词：离子液体; 氯化1-(2-丙酸基)吡啶; 杂多酸盐; 酸度; 酸催化

摘要：

设计合成氯化1-(2-丙酸基)吡啶离子液体([2-CA-PY]Cl),并通过离子交换法合成一组新型的含有羧基官能团的杂多酸盐,使用1H-NMR、IR以及XRD对合成的离子液体和杂多酸盐结构进行表征;同时,测定此类杂多酸盐的酸度及其热稳定性。结果表明:在250℃左右,合成的杂多酸盐具有较好的热稳定性;当物质量浓度为510-5 mol/L时,此类杂多酸盐都具有较强的酸度,其中1-(2-丙酸基)吡啶磷钨酸盐的酸度最高;可以作为此类杂多酸盐酸催化性能的理论依据。

Preparation of heteropolyacid salts containing carboxyl functional groups and its properties

ZHANG Leng-si¹, CHAI Wen², JI Hai-ling², LI Jing²

1. School of Petrochemical Engineering, Changzhou University, Changzhou 213164, China;
2. School of Chemistry & Materials Engineering, Changshu Institute of Technology, Changshu 215500, China

Abstract: This paper designed and synthesized the ionic liquid of chlorinated 1-(2-propionyloxy) pyridine([2-CA-PY]Cl), then exchanged the anion of the ionic liquid with heterop-olyacids to design a new kind of heteropolyacid salts containing carboxylic groups. The structures of the ionic liquid and the heteropolyacid salts were characterized by ¹H-NMR, IR or XRD spectra, and the kind of heteropolyacid salts'properties including acid strength and thermostability were tested. The study shows that all of the heteropolyacid salts had good thermostability under 250℃. 1-(2-propionyloxy) pyridine phosphotungstate performed strongest acid strength when its concentration is 5×10^-5 mol/L. In conclusion, all of the three heteropolyacid salts can be used as catalysts, the results can be used as theoretical foundation for these heteropolyacid salts in catalytic reactions.

Keywords: ionic liquid; chlorinated 1-(2-Propionyloxy) pyridine; heteropolyacid salt; acid strength; acidic catalysis

2014, 40(5): 47-51  收稿日期: 2013-12-11;收到修改稿日期: 2014-1-24

基金项目: 

作者简介: 张冷思(1988-),男,江苏盐城市人,硕士研究生,专业方向为环境友好型有机合成。

参考文献

[1] Rogers R D, Seddon K R. Ionic liquids-solvents of the future[J]. Science,2003,302:792-793.
[2] Wasserscheid P, Keim W. Ionic liquids-new "Solutions" for transition metal catalysis[J]. Angew Chem Int Ed, 2000,39(21):3772-3789.
[3] 张锁江,徐春明,吕兴梅,等. 离子液体与绿色化学[M].北京:北京科学出版社,2009:3-8.
[4] 张烨红. Keggin型杂多酸相转移催化剂的合成、表征及催化性能研究[D]. 兰州:兰州理工大学,2009.
[5] 亢世杰. 磷钨酸盐催化剂的制备表征及应用研究[D].哈尔滨:哈尔滨工程大学,2007.
[6] Zhou H Y, Gu T L, Yang D G, et al. Synthesis and characterization of novel ester functionalized chiral ionic liquids[J]. Advanced Materials Research,2011(197-198):471-477.
[7] Leng Y, Wang J, Zhu D R, et al. Polyoxometalate-based amino-functionalized ionic solid catalysts lead to highly efficient heterogeneous epoxidation of alkenes with H₂O₂[J].Green Chem,2011,12(7):1636-1639.
[8] 谢文华,叶兴凯,杨向光,等. 紫外光谱法测定杂多酸的酸强度[J]. 化学世界,1996(9):490-491.
[9] 陈静蓉. Keggin型有机膦酸-钨杂多酸的合成、表征及性质研究[D]. 广西:西南师范大学,2001.
[10] 赵亚梅,胡小玲,管萍. 离子液体1-仲丁基-3-甲基咪唑六氟磷酸盐的微波辅助合成[J]. 高等学校化学学报,2009,9(30):1814-1818.
[11] 柴文,周虞峰,陈吕莉,等. 4-甲基吡啶杂多酸盐的合成及其酯化催化性能的研究[J]. 常熟理工学院院报,2012,26(4):10-15.
[12] 赵景联,赵靓,苏慈,等. SiW12/NaY固体杂多酸催化剂的微波合成及LAS降解性能研究[J]. 化学世界,2006(6):321-324.