Review on the development of cation exchange resin's modification

doi:10.16085/j.issn.1000-6613.2016.05.030

Abstract

Abstract: Strong-acidic cation exchange resin contained a large number of strong acid groups, which renders it diversed functions of selection, exchange, absorption and catalysis, etc. But the inherent defects of poor high temperature resistance and low acid strength, make it obliged to be modified. Modified cation exchange resins have been widely used in water treatment, organic synthesis, separation and treatment, environmental protection and biological pharmaceutical, etc. The modification methods of strong-acid cation exchange resin were reviewed, mainly including: metal ion modification(Al³⁺、Sn⁴⁺、Zn²⁺、Ti⁴⁺、Fe³⁺ and Fe²⁺、Ce⁴⁺ and Ga³⁺、Ni²⁺、Zr⁴⁺、Pd²⁺, etc), sulfonation, thiol and amination modification, and other modifications, etc. The prospect of application of modified cation exchange resins was discussed. The key of the research was to prepare the resin support material with high heat resistance and chemical stability. In addition, the modification of resin was also an important method to improve its comprehensive performance and extend its applications.

Key words: cation exchange resin, support, modification, catalysis, adsorption

摘要： 强酸性阳离子交换树脂含有大量的强酸性基团,具有选择、交换、吸收和催化等功能,但其存在耐高温性能差、酸强度低等问题,故需要对其进行改性。改性的阳离子交换树脂广泛应用于水处理、有机合成、分离处理、环境保护及生物制药等领域。本文简要介绍了近年来强酸性阳离子交换树脂的改性方法,主要包含:金属离子改性(Al³⁺、Sn⁴⁺、Zn²⁺、Ti⁴⁺、Fe³⁺和Fe²⁺、Ce⁴⁺和Ga³⁺、Ni²⁺、Zr⁴⁺、Pd²⁺等)、磺化改性、巯基改性、胺化改性及其他类改性等方法;指出了其存在的问题,分析了改性阳离子交换树脂的未来发展方向,开发和研制具有耐高热和化学稳定性的树脂载体材料成为其研究的关键。除此之外,对树脂进行各种改性处理也是改善树脂综合性能、扩大其应用范围的重要方法。

关键词: 阳离子交换树脂, 载体, 改性, 催化, 吸附

CLC Number:

TQ325

CHEN Gui, XIANG Bailin, YUAN Ye, LIU Yuejin. Review on the development of cation exchange resin's modification[J]. Chemical Industry and Engineering Progress, 2016, 35(05): 1471-1476.

陈桂, 向柏霖, 袁叶, 刘跃进. 阳离子交换树脂改性研究进展[J]. 化工进展, 2016, 35(05): 1471-1476.

References

[1] 张帆, 李菁, 谭建华, 等. 吸附法处理重金属废水的研究进展[J]. 化工进展, 2013, 32(11): 2749-2755.
[2] SHI Qianqian, LI Aimin. Adsorption of naphthalene onto a high-surface-area carbon from waste ion exchange resin[J]. Journal of Environmental Sciences, 2013, 25(1): 188-194.
[3] 蔡红, 周斌. 离子交换树脂在有机催化反应中的应用进展[J]. 化工进展, 2007, 26(3): 386-391.
[4] GREG Paterson, TITIPONG Issariyakul, CHINMOY Baroi, et al. Ion-exchange resins as catalysts in transesterification of triolein[J]. Catalysis Today, 2013, 212(1): 157-163.
[5] 王信, 代龙, 孙志强, 等. 阳离子交换树脂分离纯化钩藤总生物碱的工艺研究[J]. 中草药, 2011, 42(10): 1973-1976.
[6] ZAFAR Alam, INAMUDDIN, SYED Ashfaq Nabi. Synthesis and characterization of a thermally stable strongly acidic Cd(Ⅱ) ion selective composite cation-exchanger: polyaniline Ce(Ⅳ) molybdate
[J]. Desalination, 2010, 2(15): 515-522.
[7] 毕向光, 余建民, 杨金富, 等. 阳离子树脂净化铂族金属溶液的研究[J]. 矿业工程, 2015, 35(3): 87-90, 95.
[8] FU Junying, CHEN Liangguang, LV Pengmei, et al. Free fatty acids esterification for biodiesel production using self-synthesized macroporous cation exchange resin as solid acid catalyst[J]. Fuel. 2015, 154(15): 1-8.
[9] KELA S P, KESHARWANI D. Formulation, characterization and evaluation of taste masked rapid disintegrating tablet of ofloxacin by ion exchange resin technique[J]. Intl. J. Pharm. Sci. Rev. & Res., 2013, 21(2): 246-253.
[10] PANDE S, KSHIRSAGAR M, CHANDEWAR A, et al. Ion exchange resins pharmaceutical applications and recent advancement[J]. Int. J. Adv. Pharm. Sci., 2011, 2(1): 8-16.
[11] PRINCY Gupta, SATYA Paul. Solid acids: green alternatives for acid catalysis[J]. Catalysis Today, 2014, 236: 153-170.
[12] 张秋云, 杨松, 李虎. 制备生物柴油的固体酸催化剂研究进展[J]. 化工进展, 2013, 32(3): 575-583, 591.
[13] FABREGAS Vidal, JOSE Luis. Solid pharmaceutical composition of cation exchange resin: US20150174065[P]. 2015-06-25.
[14] 裴文, 李风军, 王海滨, 等. 固体酸催化合成二芳基甲酮化合物的研究进展[J]. 有机化学, 2011, 31(8): 1188-1194.
[15] 赵志刚, 邵太丽, 秦国正. H-732阳离子交换树脂催化酯化反应[J]. 化工进展, 2012, 31(7): 1592-1596.
[16] SHU Kobayashi, TSUYOSHI Busujima, SATOSHI Nagayama. A novel classification of lewis acids on the basisi of activity and selectivity[J].Chem. Eur. J., 2000, 6(19): 2491-2494.
[17] MAGNOTTA V, GATES B. Superacid polymers: synthesis and analysis of AlCl₃-sulfonic acid resin complexes[J]. Journal of Polymer Science, 1977, 6(15): 1341-1347.
[18] 张文雯, 李运山, 何明阳, 等. 改性阳离子交换树脂催化合成双酚F[J]. 化工进展, 2007, 26(7): 26-28.
[19] 李建伟, 夏萍, 陈方平. Lewis酸型阳离子树脂催化酯化反应探讨[C]// 河南省化学会2010年学术年会暨成立70周年庆祝会论文摘要集, 南阳, 2010.
[20] 赵颖颖. 树脂改性制备新型溴吸附剂的研究[J]. 河北工业大学学报, 2015, 44(2): 95-98.
[21] 张萌萌, 谢利平, 周鹏. SnCl₄改性阳离子交换树脂催化合成柠檬酸三丁酯[J]. 精细化工, 2011, 28(8): 797-799, 802.
[22] 李瑞海, 张萌萌, 谢利平, 等. 以改性阳离子交换树脂为催化剂制备柠檬酸三丁酯的方法: 201110154724[P]. 2011-06-10.
[23] 张凤, 蒋晓原, 楼辉, 等. 微波条件下ZnCl₂改性离子交换树脂催化改质生物油的研究[J]. 燃料化学学报, 2011, 39(12): 901-906.
[24] 王茹, 唐定兴. 氧化锌/阳离子交换树脂的制备及光催化性能的研究[J]. 安徽工程大学学报, 2014, 29(3): 17-19.
[25] WANG Baohe, DONG Jinshi, CHEN Shuang. ZnCl₂-modified
ion exchange resin as an efficient catalyst for the bisphenol-
A production[J]. Chinese Chemical Letter, 2014, 25(11): 1423-1427.
[26] 王志亮. TiCl₄改性离子交换树脂催化合成甲缩醛[J]. 山东化工, 2011, 40(11): 7-8, 12.
[27] 陈桂, 王庆, 李勇飞, 等. 改性阳离子交换树脂的制备、表征及催化合成双酚F[J]. 离子交换与吸附, 2014, 30(5): 397-405.
[28] 赵文军, 汪群慧, 滕云. 催化乳酸铵酯化的改性树脂的制备与表征[J]. 材料科学与工艺, 2010, 18(1): 51-55.
[29] SYED Wasim Ali, MUHAMMAD Latif Mirza, TARIQ M Bhatti. Removal of Cr(Ⅵ) using iron nanoparticles supported on porous cation-exchange resin[J]. Hydrometallurgy, 2015, 157: 82-89.
[30] 张强, 唐定兴, 张国勇. 改性阳离子交换树脂及其制备方法和应用: 201410446111[P], 2014-09-03.
[31] WANG Qian, ZHANG Dehua, TIAN Senlin. Simultaneous adsorptive removal of methylene blue and copper ions from aqueous solution by ferrocene-modified cation exchange resin[J]. Applied Polym., 2014, 131(21): 41029.
[32] 郭鑫, 张敏卿. 大孔强酸性阳离子交换树脂催化合成柠檬酸三丁酯[J]. 化工进展, 2010, 29(4): 673-676.
[33] 陈丹云, 王海. 硫酸高铈改性离子交换树脂催化合成丙酸异戊酯[J]. 稀土, 2010, 31(2): 45-47.
[34] 周慧, 李杰, 蔡永红. 硫酸镓改性离子交换树脂催化合成异丁酸异戊酯[J]. 化工中间体, 2010, 6(3): 29-31.
[35] 蓝平, 蓝丽红, 吴如春, 等. 强酸性阳离子交换树脂负载金属离子催化制备乙酸正丙酯[J]. 化学世界, 2010, 51(12): 741-744.
[36] 李宁, 梁金花, 徐玥. 负载型CaSO₄/离子交换树脂催化合成单十二烷基磷酸酯[J]. 离子交换与吸附, 2011, 27(3): 212-218.
[37] FARANAK Sadegh, OMID Bagheri, MAJID Moghadam, et al. Palladium(II) tetrakis (4-N, N, N-trimethylammoniumpheny lene) porphyrin supported on ion-exchange resins as efficient and reusable catalysts for C-C coupling reactions[J]. Journal of Organometallic Chemistr, 2014, 759: 46-57.
[38] GUO Jintang, LIU Bing. The use of ion exchange resins in the recycle of palladium catalysts for the synthesis of polyketones[J]. Reactive & Functional Polymers, 2004, 2(61): 163-170.
[39] MARTÍN S G, BÁRBARA S S, et al. Glycerol oxidation in liquid phase: highly stable Pt catalysts supported on ion exchange resins[J]. Applied Catalysis A: General, 2015, 501: 1-9.
[40] 许平, 陈群, 何明阳, 等. 酸性阳离子交换树脂催化制备 6, 6'-二羟基-3, 3, 3', 3'-四甲基-1, 1'-螺二氢茚的工艺研究[J]. 化工进展, 2012, 31(8): 1741-1744, 1827.
[41] 马少波, 王坤, 吴晓妮, 等. 巯基助催化剂对双酚A催化剂活性影响[J]. 工业催化, 2015, 23(2): 103-105.
[42] TERAJIMA T, T TAKAI, NAKAMURA H. Modified ion exchange resin and process for producing bisphenols: US13111573[P]. 2013-04-23.
[43] 徐斌, 刘艳秋, 王俊格. 胺化改性磺酸型阳离子交换树脂酸碱协同催化环己酮自缩合反应[J]. 高校化学工程学报, 2015, 29(2): 335-340.
[44] 周彦波, 鲁军. 改性树脂处理乳化油废水及其破乳机理[J]. 沈阳大学学报(自然科学版), 2012, 24(1): 9-11, 24.
[45] 李方文, 贾海武. 阳离子表面活性剂改性树脂及处理轧钢乳化含油废水的性能[J]. 功能材料, 2011, 42(1): 50-53.
[46] HASYAGAR U K, HASYAGAR U K, MAHALINGAM R J, et al. Catalyst system comprising an ion exchange resin and a dimethyl thiazolidine promoter: EP 20120728784[P]. 2012-05-02.
[47] TERAJIMA Takashi, TAKAI Toshihiro, FUJIWARA Kenji. Method for preparing bisphenol in the presence of a modified acidic ion-exchange resin: EP 20070025003[P]. 2004-09-28.
[48] 刘野, 霍稳周, 吕清林. 一种改性阳离子交换树脂催化剂及其制备方法和应用: 201210408425[P]. 2012-10-24.