Preparation and characterization of sulfonated crosslinked chitosan resin as solid acidic catalyst

doi:10.3969/j.issn.0438-1157.2013.05.019

CIESC Journal ›› 2013, Vol. 64 ›› Issue (5): 1635-1641.DOI: 10.3969/j.issn.0438-1157.2013.05.019

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Preparation and characterization of sulfonated crosslinked chitosan resin as solid acidic catalyst

LI Junhong, XU Yuting, TANG Chengli, LIU Xiong, TAN Yunfei, DONG Lichun

School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China

Received:2012-08-19 Revised:2012-12-30 Online:2013-05-05 Published:2013-05-05
Supported by:
supported by the National Natural Science Foundation of China(2017620,51272296), the Fundamental Research Funds of Postgraduate Innovation Research for the Central Universities(CDJXS10221140, CDJXS11221169)and the National Innovation Funds for College Students(CDJXS10220006).

磺化交联壳聚糖树脂固体酸催化剂的制备及表征

李俊宏, 徐玉婷, 唐成黎, 刘雄, 谭芸妃, 董立春

重庆大学化学化工学院, 重庆 400044

通讯作者: 董立春
作者简介:李俊宏(1988-),男,硕士研究生。
基金资助:
国家自然科学基金项目(21176270,51272296);中央高校基本科研业务费科研专项"研究生科技创新基金"项目(CDJXS10221140,CDJXS11221169);大学生国家创新基金项目(CDJXS10220006)。

Abstract

Abstract: Crosslinked chitosan resins(CCRs)with different crosslinking degrees were synthesized by using the inverse emulsion method and glutaraldehyde as crosslinking agent, and then sulfonated at -5℃ with concentrated H₂SO₄ as sulfonation agent.The properties and application of obtained sulfonated crosslinked chitosan resins(SCCRs)as solid acidic catalysts were studied.IR analysis showed that sulfonation of CCR occurred at both C₂ amino groups and C₆ secondary hydroxyl groups.Sulfur content measurements demonstrated that the higher the crosslinking degree of the SCCR, the larger the sulfonation rate of its C₆ hydroxyl groups.The acidic sites in SCCR including C₆-O and C₂-N sulfate groups were all weak acidic sites.The acid content of SCCR was much higher than chitosan sulfate reported in the literature,which was prepared by direct sulfonation of chitosan without pre-crosslinking.High-temperature treatment verified that crosslinking improved the thermostability of SCCR.The SCCR with a higher crosslinking degree had better mass retention rate as well as larger sulfur retention rate.The catalytic activity and repeatability of SCCR as solid acidic catalysts were verified by testing its application in the synthesis of tributyl citrate from citric acid and butanol.The results showed that esterification rate of citrate acid could reach 94.8% when SCCR with a 100% crosslinking degree was used, and esterification rate could keep above 92% by repeated use of the SCCR for 6 times.Comparison with chitosan sulfate demonstrated that SCCR was a much better solid acidic catalyst and had a promising application prospect.

Key words: crosslinked chitosan, sulfonated crosslinked chitosan resin, solid acidic catalyst, acid content, thermostability

关键词: 交联壳聚糖, 磺化交联壳聚糖树脂, 固体酸催化剂, 酸量, 热稳定性

CLC Number:

TQ426.62

LI Junhong, XU Yuting, TANG Chengli, LIU Xiong, TAN Yunfei, DONG Lichun. Preparation and characterization of sulfonated crosslinked chitosan resin as solid acidic catalyst[J]. CIESC Journal, 2013, 64(5): 1635-1641.

李俊宏, 徐玉婷, 唐成黎, 刘雄, 谭芸妃, 董立春. 磺化交联壳聚糖树脂固体酸催化剂的制备及表征[J]. 化工学报, 2013, 64(5): 1635-1641.

References 22

[1]	Mourya V K, Inamdar N N.Chitosan-modifications and applications:opportunities galore[J].Reactive & Functional Polymers,2008,68:1013-1051
[2]	Guibal E.Heterogeneous catalysis on chitosan-based materials:a review[J].Prog. Polym. Sci.,2005, 30:71-109
[3]	Zhao Y, Tian J, Qi X, Han Z, Zhuang Y, He L. Quaternary ammonium salt-functionalized chitosan:an easily recyclable catalyst for efficient synthesis of cyclic carbonates from epoxides and carbon dioxide[J].Journal of Molecular Catalysis A:Chemical, 2007,271:284-289
[4]	Chen Hong(陈红), Zu Feng(祖峰), Hong Lian(洪莲).Study on catalytic synthesis of butyl hydroxybenzoate with chitosan sulfate[J].Journal of Anqing Teachers College:Natural Science(安庆师范学院学报:自然科学版), 2004, 10(4):4-10
[5]	Zhang Xiaoli(张晓丽), Yu Yang(于杨), Liu Di(刘迪), Liu Chunsheng(刘春生), Luo Genxiang(罗根祥).Green synthesis of n-butyl propionate catalyzed by chitosan sulfate[J].Flavour Fragrance Cosmetics(香料香精化妆品), 2007(2):14-16
[6]	Jiang Zhenju(蒋珍菊), Wang Zhouyu(王周玉), Feng Dong(冯冬).Research of sulfonated chitosan by acid[J]. Chemistry & Bioengineering(化学与生物工程), 2005(4):12-14
[7]	Wang Kejun(王科军), Xun Jun(薛珺), Wen Herui(温和瑞).Synthesis of n-butyl acetate on chitosan sulfate catalyst by microwave irradiation[J].Petrochemical Technology(石油化工), 2005, 34(4):364-367
[8]	Yu Y, He B.A new type of ALSS - the preparation of crosslinked chitosan resins and its adsorption properties for bilirubin[J].Reactive & Functional Polymers, 1996, 31:195-200
[9]	Dang Mingyan(党明岩), Zhang Yan’an(张延安), Wang Ping(王娉).Crosslinked Chitosan Resin(交联壳聚糖树脂)[M].Beijing:Chemical Industry Press, 2009
[10]	Xiao Y, Zhou X.Synthesis and properties of a novel crosslinked chitosan resin modified by L-lysine[J].Reactive & Functional Polymers, 2008,68:1281-1289
[11]	Dong L, Wang G, Xu Y, Zhou X, Xiao Y, Jiang H, Luo Q.Immobilization of glucose oxidase on a novel crosslinked chitosan support grafted with L-lysine spacers[J].Chem. Biochem. Eng. Q., 2011, 25(3):395-402
[12]	Zheng Yu(郑玉), Wang Jiye(王继叶), Tan Mingchuan(谈明传), Zheng Shiqing(郑世清).Synthesis of tributyl citrate catalyzed by tetrabutyl titanate[J].Industrial Catalysis(工业催化), 2004,12:35-37
[13]	Guo Xin(郭鑫), Zhang Minqing(张敏卿).Synthesis of tributyl citrate catalyzed by macroporous strong acid cationic exchange resin[J].Chemical Industry and Engineering Progress(化工进展), 2010, 29(1):673-676
[14]	Ning Zhengxiang(宁正祥).Analysis Manual for Food Ingredients(食品成分分析手册)[M].Beijing:China Light Industry Press, 1998
[15]	Rinaudo M.Chitin and chitosan:properties and applications[J].Prog. Polym. Sci., 2006, 31(7):603-632
[16]	Jayakumar R, Nwe N, Tokura S, Tamura H.Sulfated chitin and chitosan as novel biomaterials[J].International Journal of Biological Macromolecules,2007, 40:175-181
[17]	Xiang Y, Yang M, Guo Z, Cui Z.Alternatively chitosan sulfate blending membrane as methanol-blocking polymer electrolyte membrane for direct methanol fuel cell[J].Journal of Membrane Science,2009,337:318-323
[18]	Zhao Xia(赵侠), Yu Guangli(于广利), Lü Zhihua(吕志华).Regioselective syntheses of sulfated chitosan[J].Chinese Journal of Marine Drugs(中国海洋药物), 2002, 87:15-20
[19]	Zhou H, Qian J, Wang J, Yao W, Liu C, Chen J, Cao X.Enhanced bioactivity of bone morphogenetic protein-2 with low dose of 2-N, 6-O sulfated chitosan in vitro and in vivo[J].Biomaterials, 2009,30:1715-1724
[20]	Jiang Yuxiang(蒋玉湘).Preparation and analysis of different structure sulfated chitosan.Qingdao:Ocean University of China, 2003
[21]	Wang Bin(王斌).The study on sulfuric acid and chlorosulfonic acid esterification and surfonation of chitosan.Chengdu:Southwest Petroleum University, 2004
[22]	Crini G.Recent developments in polysaccharide-based materials used as adsorbents in wastewater treatment[J].Progress in Polymer Science, 2005, 30(1):38-70

Preparation and characterization of sulfonated crosslinked chitosan resin as solid acidic catalyst

磺化交联壳聚糖树脂固体酸催化剂的制备及表征

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