Immobilization of β-Cyclodextrin as Insoluble β-Cyclodextrin Polymer and Its Catalytic Performance

Chinese Journal of Chemical Engineering ›› 2012, Vol. 20 ›› Issue (4): 784-792.

Immobilization of β-Cyclodextrin as Insoluble β-Cyclodextrin Polymer and Its Catalytic Performance

江红果¹, 杨祖金², 周贤太², 方岩雄¹, 纪红兵²

1. Faculty of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China;
2. School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, China

收稿日期:2011-02-21 修回日期:2011-12-16 出版日期:2012-08-28 发布日期:2012-09-15
通讯作者: FANG Yanxiong, E-mail:fangyx@gdut.edu.cn;JI Hongbing, E-mail:jihb@mail.sysu.edu.cn
基金资助:
Supported by the National Natural Science Foundation of China (21036009,21176268);the Higher-level Talent Project for Guangdong Provincial Universities;the Fundamental Research Funds for the Central Universities;Guangdong Province 211 Project

Immobilization of β-Cyclodextrin as Insoluble β-Cyclodextrin Polymer and Its Catalytic Performance

JIANG Hongguo¹, YANG Zujin², ZHOU Xiantai², FANG Yanxiong¹, JI Hongbing²

1. Faculty of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China;
2. School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, China

Received:2011-02-21 Revised:2011-12-16 Online:2012-08-28 Published:2012-09-15
Supported by:
Supported by the National Natural Science Foundation of China (21036009,21176268);the Higher-level Talent Project for Guangdong Provincial Universities;the Fundamental Research Funds for the Central Universities;Guangdong Province 211 Project

摘要/Abstract

摘要： Insoluble β-cyclodextrin polymers were prepared from β-cyclodextrin(β-CD) using epichlorohydrin(EPI) as crosslinking agent under basic conditions.The polymers were characterized by Fourier Transform Infrared(FTIR),Thermogravimetry(TG),X-ray diffraction(XRD) and TG-FTIR.The results demonstrated that the polym-erization between EPI and β-CD indeed occurred,and a number of CD rings were interconnected to form a three-dimensional network.Moreover,different factors influencing the polymerization,e.g. molar ratio of EPI to β-CD,the concentration of NaOH and reaction temperature,have been investigated.The polymer prepared under the optimal conditions(the molar ratio EPI:β-CD of 44,the NaOH concentration 50% in mass,and the temperature at 65℃) showed excellent thermal stability and insolubility in organic solvents or strong acid/base.In addition,the β-cyclodextrin polymers also presented high catalytic activity for aqueous oxidation of benzyl alcohol with hy-pochlorite as oxidant.

关键词: β-cyclodextrin polymers, epichlorohydrin, polymerization, catalytic activity

Abstract: Insoluble β-cyclodextrin polymers were prepared from β-cyclodextrin(β-CD) using epichlorohydrin(EPI) as crosslinking agent under basic conditions.The polymers were characterized by Fourier Transform Infrared(FTIR),Thermogravimetry(TG),X-ray diffraction(XRD) and TG-FTIR.The results demonstrated that the polym-erization between EPI and β-CD indeed occurred,and a number of CD rings were interconnected to form a three-dimensional network.Moreover,different factors influencing the polymerization,e.g. molar ratio of EPI to β-CD,the concentration of NaOH and reaction temperature,have been investigated.The polymer prepared under the optimal conditions(the molar ratio EPI:β-CD of 44,the NaOH concentration 50% in mass,and the temperature at 65℃) showed excellent thermal stability and insolubility in organic solvents or strong acid/base.In addition,the β-cyclodextrin polymers also presented high catalytic activity for aqueous oxidation of benzyl alcohol with hy-pochlorite as oxidant.

Key words: β-cyclodextrin polymers, epichlorohydrin, polymerization, catalytic activity

江红果, 杨祖金, 周贤太, 方岩雄, 纪红兵. Immobilization of β-Cyclodextrin as Insoluble β-Cyclodextrin Polymer and Its Catalytic Performance[J]. Chinese Journal of Chemical Engineering, 2012, 20(4): 784-792.

JIANG Hongguo, YANG Zujin, ZHOU Xiantai, FANG Yanxiong, JI Hongbing. Immobilization of β-Cyclodextrin as Insoluble β-Cyclodextrin Polymer and Its Catalytic Performance[J]. Chin.J.Chem.Eng., 2012, 20(4): 784-792.

参考文献

1 Connors,K.A.,"The stability of cyclodextrin complexes in solution", Chem.Rev.,97,1325-1357(1998).
2 Szejtli,J.,"Introduction and general overview of cyclodextrin chemistry",Chem.Rev.,98,1743-1753(1998).
3 Ji,H.B.,Hang,L.Q.,Shi,D.P.,Zhou,X.T.,"β-Cyclodextrin as supermocecular catalyst in liquid-phase organic synthesis",Chin.J. Org.Chem.,28(12),2072-2080(2008).
4 Chen,H.Y.,Ji,H.B.,"Alkaline hydrolysis of cinnamaldehyde to benzaldehyde in the presence ofβ-cyclodextrin",AIChE J.,56(2),466-476(2010).
5 Shi,D.P.,Ji,H.B.,"β-Cyclodextrin promoted oxidation of aldehydes to carboxylic acids in water",Chin.Chem.Lett.,20,139-142 (2009).
6 Surendra,K.,Krishnaveni,N.S.,Rao,K.R.,"A simple biomimetic protocol for the oxidation of alcohols with sodium hypochlorite in the presence ofβ-cyclodextrin in water",Can.J.Chem.,82(7),1230-1233(2004).
7 Reddy,M.A.,Surendra,K.,Bhanumathi,N.,Rao,K.R.,"Highly facile biomimetic regio-selective ring opening of epoxides to halohydrins in the presence of β-cyclodextrin",Tetrahedron,58(30),6003-6008(2002).
8 Chan,W.K.,Yu,W.Y.,Che,C.M.,"A cyclodextrin-modified ketoester for stereo-selective epoxidation of alkenes",J.Org.Chem.,68,6576-6582(2003).
9 Ji,H.B.,Hu,X.F.,Shi,D.P.,Zhong,L.,"Controllable oxidation of sulfides to anlfoxides and sulfones with aqueous hydrogen peroxide in the presence ofβ-cyclodextrin",Russ.J.Org.Chem.,42(7),959-961(2006).
10 Ji,H.B.,Shi,D.P.,Zhong,L.,Wang,L.F.,"Transition metal-free and substrate-selective oxidation of alcohols using water as an only solvent in the presence ofβ-cyclodextrin",Tetrahedron Lett.,46(14),2517-2520(2005).
11 Ji,H.B.,"Highly shape-selective,biomimetic,and efficient deprotection of carbonyl compounds masked as ethylene acetals or dioxolanes produced from 1,2-ethanediol",Eur.J.Org.Chem.,18,3659-3662(2003).
12 Crini,G.,Morcellet,M.,"Synthesis and applications of adsorbents containing cyclodextrins",J.Sep.Sci.,25,789-813(2002).
13 Jeromin,J.,Ritter,H.,"Cyclodextrins in polymer synthesis:free radical poly-merisation of cyclodextrin complexes of cyclohexyl and phenyl methacrylate in aqueous medium",Macromol.Rapid Commun.,19,377-379(1998).
14 Seo,T.,Kajihara,T.,Iijima,T.,"The synthesis of poly(allylamine) containing covalently bound cyclodextrin and its catalytic effect in the hydrolysis of phenyl esters",Macromol.Chem.,188,2071-2082 (1987).
15 Komiyama,M.,"Selective syntheses using cyclodextrins as catalysts. V:para-selective hydroxymethylation of phenol by formaldehyde using hydroxypropyl cyclodextrins",J.Am.Chem.Soc.,11,2031-2034 (1989).
16 Veglia,A.V.,Rossi,D.R.H.,"Selectivity in the iodination of phenol in the presence ofβ-cyclodextrin".J.Org.Chem.,53,5281-5287 (1988).
17 Easton,C.J.,Licon,S.F.,Barr,L.,"Molecular reactors and machines: applications,potential,and limitations",Chem.Eur.J.,10,3120-3128 (2004).
18 Breslow,R.,Dong,S.D.,"Biemimetic reactions catalyzed by cyclodextrins and their derivatives",Chem.Rev.,98,1997-2011(1998).
19 Martel,B.,Morcellet,M.,"Cyclodextrin-poly(vinylamine)systems-Ⅱ.catalytic hydrolysis of p-nitrophenyl acetate",Eur.Polym.J.,31,1089-1093(1995).
20 Harada,A.,Fure,M.,Nozakura,S.,"Incusion of aromatic compounds by aβ-cyclodextrin-epichlorohydrin polymer",Polym.J.,13,777-781(1981).
21 Crini,G.,Bertini,S.,Torri,G.,"Sorption of aromatic compounds in water using insoluble cyclodextrin polymers",J.Appl.Polym.Sci.,68,1973-1978(1998).
22 Renard,E.,Deratani,A.,Volet,G.,Sebille,B.,"Preparation and characterization of water soluble high molecular weightβ-cyclodextrinepichlorohydrin polymers",Eur.Polym.J.,33(1),49-57(1997).
23 Solms,J.,Egli,R.H.,"Harze mit einschlusshohlraumen von cyclodextrin-struktur",Helv.Chim.Acta,48(6),1225-1228(1965).
24 Harada,A.,Furue,M.,Nozakura,S.J.,"Optical resolution of mandelic acid derivatives by column chromatography on crosslinked cyclodextrin gels",Polym.Sci.Polym.Chem.Ed.,16(1),189-196(1978).
25 Sreenivasan,K.,"Solvent effect on the interaction of steroids with a novel methylβ-cyclodextrin polymer",J.Appl.Polym.Sci.,68(11),1857-1861(1998).
26 Zohrehvand,S.,Evans,C.H.,"2-Naphthol-containingβ-cyclodextrinepichlorohydrin copolymers:synthesis,characterization and fluorescence studies",Polym.Inter.,54(5),744-753(2005).
27 Nozaki,T.,Maeda,Y.,Kitano,H.,"Cyclodextrin gels which have a temperature respon-siveness",J.Polym.Sci.Pol.Chem.,35(8),1535-1541(1997).
28 Crini,G.,Janus,L.,Morcellet,M.,Torri,G.,"Macroporous polyamines containing cyclo-dextrin:synthesis,characterization and sorption properties",J.Appl.Polym.Sci.,69(7),1419-1427(1998).
29 Szejtli,J.,Fenyvesi,E.,Zsadon,B.,"Cyclodextrinpolymere",Starch,30(4),127-131(1978).
30 Crini,G.,Cosentino,C.,Bertini,S.,Naggi,A.,Torri,G.,Vecchi,C., Janus,L.,Morcellet,M.,"Solid state NMR spectroscopy study of molecular motions in cyclomaltoheptaose(β-cyclodextrin)crosslinked with epichlorhydrin",Carbohydr.Res.,308(1-2),37-45(1998).
31 Crini,G.,Bourdonneau,M.,Martel,B.,Piotto,M.,Morcellet, M.,Richert,T.,Vebrel,J.,Torri,G.,Morin,N.,"Solid-state NMR characterization of cyclomaltoheptaose(β-cyclodextrin)polymers using high-resolution magic angle spinning with gradients",Appl. Polym.Sci.,75(10),1288-1295(2000).
32 Yu,J.C.,Jiang,Z.T.,Liu,H.Y.,Liu,J.,Zhang,L.Z.,"β-Cyclodextrin epichlorohydrin copolymer as a solid-phase extraction adsorbent for aromatic compounds in waters samples",Anal.Chim.Acta,477(1),93-101(2003).
33 Romo,A.,Penas,F.J.,Isasi,J.R.,"Sorption of dibenzofuran derivatives from aqueous solutions byβ-cyclodextrin polymers:An isosteric heat approach",J.Colloid.Interf.Sci.,279(1),55-60(2004).
34 Vélaz,I.,Isasi,J.R.,Sánchez,M.,Uzqueda,M.,Ponchel,G.,"Structural characteristics of some soluble and insolubleβ-cyclodextrin polymers", J.Inclusion Phenom.Mol.Recognit.Chem.,57(1-4),65-68(2007).
35 Yudiarto,A.,Kashiwabara,S.,Tashiro,Y.,Kokugan,T.,"Separation of structural isomers using solubleβ-cyclodextrin polymer by ultrafiltration",Sep.Pur.Technol.,24(1-2),243-253(2001).
36 Gaidamauskas,E.,Norkus,E.,Butkus,E.,"Deprotonation of β-cyclodextrin alkaline solutions",Carbohydr.Res.,344(2),250-254 (2009).
37 Hanabusa,K.,Tsutsumi,H.,Kurose,A.,Shirai,H.,Hayakawa,T., Hojo,N.,"Synthesis of poly(amino acid)s on molecular assemblies formed by functional active esters of amino acids",J.Polym.Sci.A Polym.Chem.,27(5),191-195(1989).
38 Delval,F.,Crini,G.,Bertini,S.,Crini,N.M.,Badot,P.M.,Vebrel,J., Torri,G.,"Characterization of crosslinked starch materials with spectroscopic techniques",J.Appl.Polym.Sci.,93(6),2650-2663 (2004).
39 Flores,J.,Jiméne,V.,Belmar,J.,Mansilla H.D.,Alderete J.B.,"Inclusion complexation of phenol derivatives with aβ-cyclodextrin based polymer",J.Incl.Phenom.Macrocycl.Chem.,53(1-2),63-68 (2005).
40 Pekel,N.,Sahiner,N.,Güven,O.,Rzaev,Z.M.O.,"Synthesis and characterization of N-vinylimidazole-ethyl methacrylate copolymers and determination of monomer reactivity ratios",Eur.Polym.J.,37 (12),2443-2451(2001).
41 Girek,T.,Shin,D.H.,Lim,S.T.,"Polymerization ofβ-cyclodextrin with maleic anhydride and structural characterization of the polymers",Carbohydr.Polym.,42(1),59-63(2000).

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Immobilization of β-Cyclodextrin as Insoluble β-Cyclodextrin Polymer and Its Catalytic Performance

Immobilization of β-Cyclodextrin as Insoluble β-Cyclodextrin Polymer and Its Catalytic Performance

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