点击化学法制备SBS-TMA型阴离子交换膜及其性能
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摘要
以聚苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)为基质、炔丙基三甲胺盐(PTMA)为碱性功能基团,通过点击化学(click chemistry)法合成聚合物SBS-TMA,采用浇铸成膜法制得扩散渗析(DD)性能优异的均质型阴离子交换膜。借助核磁共振仪(1H NMR)、扫描电镜(SEM)对聚合物的结构、形貌表征;借助热重分析仪(TG)、精密天平对膜的热、酸性稳定性能表征。研究了功能基团含量和温度双重因素对其DD性能的影响,结果表明:在室温下,当功能基团的含量为0.20(即SBS-TMA-0.20)时,膜的扩散系数(UH+)为2.86×10-2m/h,分离系数(S)为28.1,该膜的DD性能是商业膜DF-120(UH+=9×10~(–3)m/h,S=18)的2~3倍;当系统温度由25℃升至70℃时,膜SBS-TMA-0.20的UH+值由2.86×10~(–2)m/h增加至4.48×10~(–2)m/h,它的S值由28.1增加至30.1,随后由30.1快速下降至16.2。
Homogeneous anion-exchange membrane featured with excellent efficacy of diffusion dialysis(DD)is prepared through casting process for modeling membrane method.The matrix is the segmented copolymer formed from polystyrene-butadiene-styrene and propargyl trimethylamine is adopted as the alkaline functional group.The synthesis of polymer SBS-TMA is achieved by click chemistry process.The chemical structure and morphology of the polymer are characterized by ~1H NMR spectroscopy(~1H NMR)and scanning electron microscopy(SEM).With the help of thermal gravimetric(TG)analyzer and precision balance,thermal and acidic stability of the membrane are studied.We have explored the impacts of the content of functional groups and temperature on its DD property.The results show that,when the content of functional group is 0.20(SBS-TMA-0.20),the diffusion coefficient(U H+)for the membrane is 2.86×10~(–2) m/h,and the separation coefficient(S)is 28.1.The DD property of this membrane is twice to three times as good as that of the commercial membrane DF-120.When the system temperature rises from 25℃ to 70℃,the UH+ of SBS-TMA-0.20 increases from 2.86×10~(–2) m/h to 4.48×10~(–2) m/h accordingly,and its S increases from 28.1 to 30.1,but then sharply reduces to 16.2.
Homogeneous anion-exchange membrane featured with excellent efficacy of diffusion dialysis(DD)is prepared through casting process for modeling membrane method.The matrix is the segmented copolymer formed from polystyrene-butadiene-styrene and propargyl trimethylamine is adopted as the alkaline functional group.The synthesis of polymer SBS-TMA is achieved by click chemistry process.The chemical structure and morphology of the polymer are characterized by ~1H NMR spectroscopy(~1H NMR)and scanning electron microscopy(SEM).With the help of thermal gravimetric(TG)analyzer and precision balance,thermal and acidic stability of the membrane are studied.We have explored the impacts of the content of functional groups and temperature on its DD property.The results show that,when the content of functional group is 0.20(SBS-TMA-0.20),the diffusion coefficient(U H+)for the membrane is 2.86×10~(–2) m/h,and the separation coefficient(S)is 28.1.The DD property of this membrane is twice to three times as good as that of the commercial membrane DF-120.When the system temperature rises from 25℃ to 70℃,the UH+ of SBS-TMA-0.20 increases from 2.86×10~(–2) m/h to 4.48×10~(–2) m/h accordingly,and its S increases from 28.1 to 30.1,but then sharply reduces to 16.2.
引文
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[18]MOHANTY A D,RYU C Y,KIM Y S,et al.Stable elastomeric anion exchange membranes based on quaternary ammonium-tethered polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene triblock copolymers[J].Macromolecules,2015,48(19):7085-7095.
[19]LIN X C,SHAMSAEI E,KONG B,et al.Fabrication of asymmetrical diffusion dialysis membranes for rapid acid recovery with high purity[J].Journal of Materials Chemistry A,2015,3(47):24000-24007.
[20]EMMANUEL K,CHENG C L,ERIGENE B,et al.Imidazolium functionalized anion exchange membrane blended with PVA for acid recovery via diffusion dialysis process[J].Journal of Membrane Science,2016,49(7):209-215.
[2]KOBUCHI Y,MOTOMURA H,NOMA Y,et al.Application of ion exchange membranes to the recovery of acids by diffusion dialysis[J].Journal of Membrane Science,1986,27(2):173-179.
[3]ZHELEZNOV A,WINDMOLLER D,KORNER S,et al.Dialytic transport of carboxylic acids through an anion exchange membrane[J].Journal of Membrane Science,1998,139(1):137-143.
[4]兰生杰,温现明,祝增虎.工业酸性废液回收利用的现状[J].无机盐工业,2010(7):9-11.LAN S J,WEN X M,ZHU Z H.The situation of recycle of industrial acidic liquid waste[J].Inorganic Chemicals Industry,2010(7):9-11.
[5]LUO J Y,WU C M,XU T W,et al.Diffusion dialysis-concept,principle and applications[J].Journal of Membrane Science,2011,366(1/2):1-16.
[6]OH S J,MOON S H,DAVIS T.Effects of metal ions on diffusion dialysis of inorganic acids[J].Journal of Membrane Science,2000,169(1):95-105.
[7]XU T W,YANG W.Tuning the diffusion dialysis performance by surface cross-linking of PPO anion exchange membranessimultaneous recovery of sulfuric acid and nickel from electrolysis spent liquor of relatively low acid concentration[J].Journal of Hazardous Materials,2004,109(1-3):157-164.
[8]张绍玲,徐铜文,刘兆明.阴离子交换膜的制备和改性研究进展[J].离子交换与吸附,2006,22(4):375-384.ZHANG S L,XU T W,LIU Z M.Research progress on preparation and modification of anion-exchange membrane[J].Ion Exchange and Adsorption,2006,22(4):375-384.
[9]XU T W,LIU Z M,LI Y,et al.Preparation and characterization of type II anion exchange membranes from poly(2,6-dimethyl-1,4-phenylene oxide)(PPO)[J].Journal of Membrane Science,2008,320(1/2):232-239.
[10]KUMAR G G,NAHM K,ELIZABETH R N.Structural,thermal and ion transport studies of different particle size nanocomposite fillers incorporated PVDF-HFP hybrid membranes[J].Materials Chemistry and Physics,2009,115(1):40-46.
[11]李娟,段明,张烈辉,等.点击化学及其应用[J].化学进展,2007,19(11):1754-1760.LI J,DUAN M,ZHANG L H,et al.Click chemistry and its application[J].Progress in Chemical,2007,19(11):1754-1760.
[12]邱素艳,高森,林振宇,等.点击化学最新进展[J].化学进展,2011,23(4):637-648.QIU S Y,GAO S,LIN Z Y,et al.Click chemistry is reviewed[J].Progress in Chemical,2011,23(4):637-648.
[13]HU C,GUO X,JING Y,et al.Structure and mechanical properties of crosslinked glycidyl azide polymers via click chemistry as potential binder of solid propellant[J].Journal of Applied Polymer Science,2014,131(16):318-323.
[14]LI N W,GUIVER M D,BINDER W H.Towards high conductivity in anion-exchange membranes for alkaline fuel cells[J].Chem Sus Chem,2013,6(8):1376-83.
[15]王勃,沈大明.热塑弹性体SBS的改性研究进展[J].粘接,2005,26(2):24-28.WANG B,SHEN D M.Research progress of modification of thermoplastic elastomer SBS[J].Adhesion,2005,26(2):24-28.
[16]HE Y B,PAN J F,WU L,et al.Facile preparation of1,8-diazabicyclo[5.4.0]undec-7-ene based high performance anion exchange membranes for diffusion dialysis applications[J].Journal of Membrane Science,2015,49(1):45-52.
[17]WU L,PAN Q,VARCOE J R,et al.Thermal crosslinking of an alkaline anion exchange membrane bearing unsaturated side chains[J].Journal of Membrane Science,2015,49(1):1-8.
[18]MOHANTY A D,RYU C Y,KIM Y S,et al.Stable elastomeric anion exchange membranes based on quaternary ammonium-tethered polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene triblock copolymers[J].Macromolecules,2015,48(19):7085-7095.
[19]LIN X C,SHAMSAEI E,KONG B,et al.Fabrication of asymmetrical diffusion dialysis membranes for rapid acid recovery with high purity[J].Journal of Materials Chemistry A,2015,3(47):24000-24007.
[20]EMMANUEL K,CHENG C L,ERIGENE B,et al.Imidazolium functionalized anion exchange membrane blended with PVA for acid recovery via diffusion dialysis process[J].Journal of Membrane Science,2016,49(7):209-215.