系列N-烷基吡啶氯盐的合成、表征及在双水相中液/液/固边界线的研究
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摘要
采用一步法合成N-正乙基吡啶氯盐(N-ethyl pyridine chlorine salt,EPyCl)、N-正丁基吡啶氯盐(N-butyl pyridine chlorine salt,BPyCl)、N-正己基吡啶氯盐(N-hexyl pyridine chlorine salt,HPyCl),并通过差示扫描量热法(differential scanning calorimetry,DSC)表征产物纯度。运用单因素试验研究各因素对产物得率的影响,并通过L_9(3~4)正交表优化合成条件。将合成的吡啶氯盐应用于[C_nPy]Cl(n=2、4、6)-K_2HPO_4双水相体系,分别用清-浊点辅助法、相转变法研究双水相相图及液/液/固边界线。结果表明:3种产物得率分别为:92.42%、90.07%、85.67%,且DSC表征后,纯度理想。最佳合成条件为反应温度80℃、时间72 h、配料摩尔比(吡啶∶氯代烷)=1.0∶1.2及溶剂乙酸乙酯用量100 mL。Merchuk方程关联的双节线数据的拟合度在0.996以上,结果理想。侧烷基链长度及体系温度的改变均影响液/液/固边界线。试验结果为此类双水相相图研究提供了理论依据。
The N-ethyl pyridine chlorine salt(EPyCl),N-butyl pyridine chlorine salt(BPyCl),N-hexyl pyridine chlorine salt(HPyCl) were synthesized by one-step method. The purity of three products were characterized by differential scanning calorimetry(DSC). The single factor experiments were used to study the influences of different factors on the yield of products. The L_9(3~4)orthogonal table was used to optimize the synthesis conditions. The three pyridine chlorine salts were applied to the [C_nPy]Cl(n =2,4,6)-K_2HPO_4 aqueous two-phase system. The binodal curve was measured by means of clear-cloud points aid and the liquid/liquid/solid boundary line was studied by the phase shift method. Results showed that:these products yield were 92.42 %,90.07 %,85.67 % respectively. The three products were characterized by DSC and the purity of them were ideal. The optimal synthesis conditions were reaction temperature 80 ℃,time 72 h,dosing molar ratio(pyridine ∶ chloralkane)= 1.0 ∶ 1.2 and the dosage of ethyl acetate solvent 100 mL. The data fitting of binodal curve was based on Merchuk equation and the fitting degree was above 0.996,which was ideal. The change of alkyl chain length and temperature were influential to liquid/liquid/solid boundary line. The result provided a theoretical basis for the study of the phase diagram of these aqueous two-phase systems.
The N-ethyl pyridine chlorine salt(EPyCl),N-butyl pyridine chlorine salt(BPyCl),N-hexyl pyridine chlorine salt(HPyCl) were synthesized by one-step method. The purity of three products were characterized by differential scanning calorimetry(DSC). The single factor experiments were used to study the influences of different factors on the yield of products. The L_9(3~4)orthogonal table was used to optimize the synthesis conditions. The three pyridine chlorine salts were applied to the [C_nPy]Cl(n =2,4,6)-K_2HPO_4 aqueous two-phase system. The binodal curve was measured by means of clear-cloud points aid and the liquid/liquid/solid boundary line was studied by the phase shift method. Results showed that:these products yield were 92.42 %,90.07 %,85.67 % respectively. The three products were characterized by DSC and the purity of them were ideal. The optimal synthesis conditions were reaction temperature 80 ℃,time 72 h,dosing molar ratio(pyridine ∶ chloralkane)= 1.0 ∶ 1.2 and the dosage of ethyl acetate solvent 100 mL. The data fitting of binodal curve was based on Merchuk equation and the fitting degree was above 0.996,which was ideal. The change of alkyl chain length and temperature were influential to liquid/liquid/solid boundary line. The result provided a theoretical basis for the study of the phase diagram of these aqueous two-phase systems.
引文
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[31]LI Y L,Zhong Y X,Qin X L,et al.Phase diagram of ionic liquid aqueous two-phase systems with N-butylpyridinium tetrafluoroborate,ammonium Citrate/Sodium acetate,and water from 308.15K to328.15K[J].Thermochimica Acta,2016,632:72-78
[32]LI W X,Sun D Z,Zhang T,et al.Separation of acetone and methanol azeotropic system using ionic liquid as entrainer[J].Fluid Phase Equilibria,2014,383:182-187
[33]孟瑞.离子液体-Rb2CO3/Cs2CO3新型双水相体系的相行为及其在L-色氨酸分离富集中的应用[D].西安:陕西师范大学,2012
[34]张香平,白银鸽,闫瑞一,等.离子液体萃取分离有机物研究进展[J].化工进展,2016,35(6):1587-1605
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[2]Malekghasemi S,Mokhtarani B,Hamzehzadeh S,et al.Liquid-liquid equilibria of aqueous biphasic systems of ionic liquids and dipotassium hydrogen phosphate at different temperatures:Experimental study and thermodynamic modeling[J].Journal of Molecular Liquids,2016,219:95-103
[3]Jahani F,Abdollahifar M,Haghnazari N.Thermodynamic equilibrium of the polyethylene glycol 2000 and sulphate salts solutions[J].Journal of Chemical Thermodynamics,2014,69(5):125-131
[4]Herrera A,Boussiba S,Napoleone V,et al.Recovery of c-phycocyanin from the cyanobacterium Spirulina maxima[J].Journal of Applied Phycology,1989,1(4):325-331
[5]Cole K D.Purification of plasmid and high molecular mass DNA using PEG-salt two phase extraction[J].Biotechniques,1991,11(1):18-20,22
[6]Li Z,Pei Y,Wang H,et al.Ionic liquid-based aqueous two-phase systems and their applications in green separation processes[J].Trac Trends in Analytical Chemistry,2010,29(11):1336-1346
[7]He Y,Chik S M S B T,Chong F C.Purification of papain from unclarified papaya juice using reversed phase expanded bed adsorption chromatography(RP-EBAC)[J].Journal of Industrial and Engineering Chemistry,2014,20(6):4293-4297
[8]Vicente F A,Lario L D,Jr A P,et al.Recovery of bromelain from pineapple stem residues using aqueous micellar two-phase systems with ionic liquids as co-surfactants[J].Process Biochemistry,2016,51(4):528-534
[9]FAN Y C,DONG X,YAN L L,et al.Evaluation of the toxicity of ionic liquid on trypsin:A mechanism study[J].Chemosphere,2016,148:241-247
[10]Mirjana A,Radovan O.Pectinase partitioning in polyethylene glycol1000/Na2SO4 aqueous two-phase system:statistical modeling of the experimental results[J].Bioprocess Biosyst Eng,2009,32:235-240
[11]Corderí S,Gómez E,Angeles Domínguez,et al.(Liquid+liquid)equilibrium of ternary and quaternary systems containing heptane,cyclohexane,toluene and the ionic liquid[Emim][N(CN)2].Experimental data and correlation[J].Journal of Chemical Thermodynamics,2016,94:16-23
[12]王伟涛,张海德,蒋志国,等.离子液体双水相提取木瓜蛋白酶及条件优化[J].现代食品科技,2014(9):210-216
[13]刘曼,施敏,曹学丽.离子液体双水相萃取-HPLC分析红酒中的痕量氯酚类物质[J].食品科学,2017,38(12):260-265
[14]南二龙.亲水有机溶剂/盐双水相体系中液/液/固边界线的研究及相比数据库的建立[D].上海:东华大学,2014
[15]Jiang X M,Lu Y M,Tan C P,et al.Combination of aqueous twophase extraction and cation-exchange chromatography:new strategies for separation and purification of alliin from garlic powder[J].Journal of Chromatography B Analytical Technologies in the Biomedical&Life Sciences,2014,957:60-67
[16]Nemati-Knade E,Shekaari H,Jafari S A.Thermodynamic study of aqueous two phase systems for some aliphatic alcohols+sodium thiosulfate+water[J].Fluid Phase Equilibria,2012,321:64-72
[17]张海德,王伟涛,蒋欣欣.木瓜蛋白酶在亲和双水相系统中的分配行为及机制研究进展[J].食品安全质量检测学报,2013(2):328-332
[18]范芳芳,卢昶雨.离子液体分离体系的研究与发展[J].应用化工,2013,42(7):1300-1304
[19]吴丁丁,穆小静,易小琦,等.双水相萃取技术的新发展[J].食品工业科技,2017,38(8):395-400
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[22]彭全明,王磊,于娜,等.N-正丁基吡啶四氟硼酸盐离子液体的合成[J].应用技术学报,2014,14(1):20-23
[23]赵春深,宋吾燕,吴昌云,等.4-氟-2-氨基吡啶的合成研究[J].广东化工,2013,40(17):229-230
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[27]Michal Ceglowski,Grzegorz Schroeder.Removal of heavy metal ions with the use of chelating polymers obtained by grafting pyridinepyrazole ligands onto polymethylhydrosiloxane[J].Chemical Engineering Journal,2015,259:885-893
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[29]Karaaggac D,Kürkcüogglu G S,enyel M,et al.Syntheses,structural characterization and spectroscopic studies of cadmium(II)-metal(II)cyanide complexes with 4-(2-aminoethyl)pyridine[J].Journal of Molecular Structure,2017,1130:80-88
[30]马海霞.三唑酮及其盐的合成、结构、热分解机理、非等温热分解反应动力学及理论研究[D].西安:西北大学,2004
[31]LI Y L,Zhong Y X,Qin X L,et al.Phase diagram of ionic liquid aqueous two-phase systems with N-butylpyridinium tetrafluoroborate,ammonium Citrate/Sodium acetate,and water from 308.15K to328.15K[J].Thermochimica Acta,2016,632:72-78
[32]LI W X,Sun D Z,Zhang T,et al.Separation of acetone and methanol azeotropic system using ionic liquid as entrainer[J].Fluid Phase Equilibria,2014,383:182-187
[33]孟瑞.离子液体-Rb2CO3/Cs2CO3新型双水相体系的相行为及其在L-色氨酸分离富集中的应用[D].西安:陕西师范大学,2012
[34]张香平,白银鸽,闫瑞一,等.离子液体萃取分离有机物研究进展[J].化工进展,2016,35(6):1587-1605
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