PDMAEMA改性PEBA/PSF复合膜的制备及其渗透汽化分离性能
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摘要
为了改进聚醚嵌段酰胺(PEBA)/聚砜(PSF)膜的透水性,采用共混聚甲基丙烯酸-N,N-二甲氨基乙酯(PDMAEMA)的方法,通过季胺化交联反应在膜内固定水溶性的PDMAEMA,使其在使用中不至于溶出,制备出PDMAEMA-PEBA/PSF复合膜,并用于乙二醇脱水,考察了不同共混含量对膜渗透汽化脱水性能的影响,通过析因设计探究了交联条件(交联剂种类、交联剂浓度、交联时间)对膜渗透选择性能的影响,遴选出能够使共混膜具有良好渗透选择性能的交联条件,并对改性后膜的表面性质进行了研究.结果表明:当聚合物质量浓度为10 g/L、PDMAEMA质量分数为15%~25%时,共混膜与PEBA/PSF膜相比,水通量提高了约80%,水/乙二醇分离因子提高了约40%;共混改性后膜表面亲水性增加,平均粗糙度增加了约120%,纯水接触角下降了约7°.
In order to improve the water permeability of polyether block amide(PEBA)/polysulfone(PSF) membrane, the method of blended poly-N,N-dimethylaminoethyl methacrylate(PDMAEMA) was used. PDMAEMA-PEBA/PSF composite membrane was prepared by quaternization crosslinking reaction to fix water soluble PDMAEMA in the membrane to avoid dissolution, and the membrane was used for ethylene glycol dehydration. The influence of blending content on pervaporation dehydration performance of the membrane was investigated. The effects of cross-linking conditions(including species of cross-linking agent, concentration of cross-linking agent, and crosslinking time) on the membrane permselectivity were explored by factorial design. A suitable cross-linking condition for making the blended membrane with a good permselectivity was selected. And the surface properties of the modified membrane were studied. The results showed that when the polymer content was 10 g/L and the content of PDMAEMA was 15%-25%, compared with PEBA/PSF membrane, the water flux increased by about80%, water/glycol separation factor increased by about 40%. The surface hydrophilicity of modified blended membrane increaseed, the average roughness increased by about 120%, the contact angle of pure water decreased by about 7°.
In order to improve the water permeability of polyether block amide(PEBA)/polysulfone(PSF) membrane, the method of blended poly-N,N-dimethylaminoethyl methacrylate(PDMAEMA) was used. PDMAEMA-PEBA/PSF composite membrane was prepared by quaternization crosslinking reaction to fix water soluble PDMAEMA in the membrane to avoid dissolution, and the membrane was used for ethylene glycol dehydration. The influence of blending content on pervaporation dehydration performance of the membrane was investigated. The effects of cross-linking conditions(including species of cross-linking agent, concentration of cross-linking agent, and crosslinking time) on the membrane permselectivity were explored by factorial design. A suitable cross-linking condition for making the blended membrane with a good permselectivity was selected. And the surface properties of the modified membrane were studied. The results showed that when the polymer content was 10 g/L and the content of PDMAEMA was 15%-25%, compared with PEBA/PSF membrane, the water flux increased by about80%, water/glycol separation factor increased by about 40%. The surface hydrophilicity of modified blended membrane increaseed, the average roughness increased by about 120%, the contact angle of pure water decreased by about 7°.
引文
[1]BAKER R W.Research needs in the membrane separation industry:Looking back,looking forward[J].Journal of Membrane Science,2010,362(1/2):134-136.
[2]李继定,杨正,金夏阳,等.渗透汽化膜技术及其应用[J].中国工程科学,2014,16(12):46-51.LI J D,YANG Z,JIN X Y,et al.Pervaporation membrane technology and its application[J].Engineering Sciences,2014,16(12):46-51(in Chinese).
[3]张秀华,朱爱梅,张秋根,等.聚乙烯醇/聚乙烯吡咯烷酮共混膜的制备和性能[J].高分子材料科学与工程,2010(9):146-150.ZHANG X H,ZHU A M,ZHANG Q G,et al.Poly(Vinyl Alcohol)/polyvinylpyrrolidone blending membranes:Preparation,characterization[J].Polymer Materials Science&Engineering,2010(9):146-150(in Chinese).
[4]LIU G,WEI W,WU H,et al.Pervaporation performance of PDMS/ceramic composite membrane in acetone butanol ethanol(ABE)fermentation-PV coupled process[J].Fuel&Energy Abstracts,2011,373(1):121-129.
[5]XIA S,DONG X,ZHU Y,et al.Dehydration of ethyl acetatewater mixtures using PVA/ceramic composite pervaporation membrane[J].Separation&Purification Technology,2011,77(1):53-59.
[6]LIU G,WANG W,HAO W,et al.Pervaporation performance of PDMS/ceramic composite membrane in acetone butanol ethanol(ABE)fermentation-PV coupled process[J].Journal of Membrane Science,2011,373(1):121-129.
[7]HAO L,LI P,CHUNG T S.PIM-1 as an organic filler to enhance the gas separation performance of ultempolyetherimide[J].Journal of Membrane Science,2014,453(3):614-623.
[8]BASTANI D,ESMAEILI N,ASADOLLAHI M.Polymeric mixed matrix membranes containing zeolites as a filler for gas separation applications:A review[J].Journal of Industrial&Engineering Chemistry,2013,19(2):375-393.
[9]ADAMS R,CARSON C,WARD J,et al.Metal organic fra-mework mixed matrix membranes for gas separations[J].Microporous&Mesoporous Materials,2010,131(1):13-20.
[10]KIM W G,NAIR S.Membranes from nanoporous 1D and 2D materials:A review of opportunities,developments,and challenges[J].Chemical Engineering Science,2013,104(50):908-924.
[11]KIM S,PECHAR T W,MARAND E.Poly(imide siloxane)and carbon nanotubemixed matrix membranes for gas separation[J].Desalination,2006,192(1):330-339.
[12]刘迪,任吉中,邓麦村.聚醚共聚酰胺复合气体分离膜的制备与分离性能[J].膜科学与技术,2010,30(3):44-49.LIU D,REN J Z,DENG M C.Preparation of poly(ether block amide)composite gas separation membranes and their performance[J].Membrane Science and Technology,2010,30(3):44-49(in Chinese).
[13]SZWAST M,MAKARUK A,HARASEK M.Gas separation membranes made of PEBA block copolymer[J].Architecture Civil Engineering Environment,2012,5(4):107-111.
[14]SHANGGUAN Y Y.Intrinsic properties of poly(Ether-B-Amide)(PEBAXR1074)for gas permeation and pervaporation[D].Waterloo,Ontario:University of Waterloo,2011.
[15]苗成朋.不对称静电场耦合膜法气体脱湿过程[D].天津:天津工业大学,2015.MIAO C P.Membrane gas dehydration in a pressure-electric coupled field[D].Tianjin:Tianjin Polytechnic University,2015(in Chinese).
[16]DU R,FENG X,CHAKMA A.Poly(N,N-dimethylaminoethyl methacrylate)/polysulfone composite membranes for gas separations[J].Journal of Membrane Science,2006,279(1):76-85.
[17]YANG Y F,WAN L S,XU Z K.Surface hydrophilization for polypropylene microporous membranes:A facile interfacial crosslinking approach[J].Journal of Membrane Science,2009,326(2):372-381.
[18]DU J R,CHAKMA A,FENG X.Dehydration of ethylene glycol by pervaporation using poly(N,N-dimethylaminoethylmethacrylate)/polysulfone composite membranes[J].Separation&Purification Technology,2008,64(1):63-70.
[19]李笑笑,张赞赞,党杰,等.析因设计研究聚乙烯醇对聚偏氟乙烯多孔膜表面涂层改性[J].膜科学与技术,2017,37(4):33-37.LI X X,ZHANG Z Z,DANG J,et al.Modification of poly(vinylidene fluoride)porous membranes by surface coating with poly(vinyl alcohol)on the basis of factorial design[J].Membrane Science and Technology,2017,37(4):33-37(in Chinese).
[20]史新洋.不对称静电场耦合气体分离过程[D].天津:天津工业大学,2014.SHI X Y.Membrane gas dehydration in a pressure-electric coupled field[D].Tianjin:Tianjin Polytechnic University,2014(in Chinese).
[2]李继定,杨正,金夏阳,等.渗透汽化膜技术及其应用[J].中国工程科学,2014,16(12):46-51.LI J D,YANG Z,JIN X Y,et al.Pervaporation membrane technology and its application[J].Engineering Sciences,2014,16(12):46-51(in Chinese).
[3]张秀华,朱爱梅,张秋根,等.聚乙烯醇/聚乙烯吡咯烷酮共混膜的制备和性能[J].高分子材料科学与工程,2010(9):146-150.ZHANG X H,ZHU A M,ZHANG Q G,et al.Poly(Vinyl Alcohol)/polyvinylpyrrolidone blending membranes:Preparation,characterization[J].Polymer Materials Science&Engineering,2010(9):146-150(in Chinese).
[4]LIU G,WEI W,WU H,et al.Pervaporation performance of PDMS/ceramic composite membrane in acetone butanol ethanol(ABE)fermentation-PV coupled process[J].Fuel&Energy Abstracts,2011,373(1):121-129.
[5]XIA S,DONG X,ZHU Y,et al.Dehydration of ethyl acetatewater mixtures using PVA/ceramic composite pervaporation membrane[J].Separation&Purification Technology,2011,77(1):53-59.
[6]LIU G,WANG W,HAO W,et al.Pervaporation performance of PDMS/ceramic composite membrane in acetone butanol ethanol(ABE)fermentation-PV coupled process[J].Journal of Membrane Science,2011,373(1):121-129.
[7]HAO L,LI P,CHUNG T S.PIM-1 as an organic filler to enhance the gas separation performance of ultempolyetherimide[J].Journal of Membrane Science,2014,453(3):614-623.
[8]BASTANI D,ESMAEILI N,ASADOLLAHI M.Polymeric mixed matrix membranes containing zeolites as a filler for gas separation applications:A review[J].Journal of Industrial&Engineering Chemistry,2013,19(2):375-393.
[9]ADAMS R,CARSON C,WARD J,et al.Metal organic fra-mework mixed matrix membranes for gas separations[J].Microporous&Mesoporous Materials,2010,131(1):13-20.
[10]KIM W G,NAIR S.Membranes from nanoporous 1D and 2D materials:A review of opportunities,developments,and challenges[J].Chemical Engineering Science,2013,104(50):908-924.
[11]KIM S,PECHAR T W,MARAND E.Poly(imide siloxane)and carbon nanotubemixed matrix membranes for gas separation[J].Desalination,2006,192(1):330-339.
[12]刘迪,任吉中,邓麦村.聚醚共聚酰胺复合气体分离膜的制备与分离性能[J].膜科学与技术,2010,30(3):44-49.LIU D,REN J Z,DENG M C.Preparation of poly(ether block amide)composite gas separation membranes and their performance[J].Membrane Science and Technology,2010,30(3):44-49(in Chinese).
[13]SZWAST M,MAKARUK A,HARASEK M.Gas separation membranes made of PEBA block copolymer[J].Architecture Civil Engineering Environment,2012,5(4):107-111.
[14]SHANGGUAN Y Y.Intrinsic properties of poly(Ether-B-Amide)(PEBAXR1074)for gas permeation and pervaporation[D].Waterloo,Ontario:University of Waterloo,2011.
[15]苗成朋.不对称静电场耦合膜法气体脱湿过程[D].天津:天津工业大学,2015.MIAO C P.Membrane gas dehydration in a pressure-electric coupled field[D].Tianjin:Tianjin Polytechnic University,2015(in Chinese).
[16]DU R,FENG X,CHAKMA A.Poly(N,N-dimethylaminoethyl methacrylate)/polysulfone composite membranes for gas separations[J].Journal of Membrane Science,2006,279(1):76-85.
[17]YANG Y F,WAN L S,XU Z K.Surface hydrophilization for polypropylene microporous membranes:A facile interfacial crosslinking approach[J].Journal of Membrane Science,2009,326(2):372-381.
[18]DU J R,CHAKMA A,FENG X.Dehydration of ethylene glycol by pervaporation using poly(N,N-dimethylaminoethylmethacrylate)/polysulfone composite membranes[J].Separation&Purification Technology,2008,64(1):63-70.
[19]李笑笑,张赞赞,党杰,等.析因设计研究聚乙烯醇对聚偏氟乙烯多孔膜表面涂层改性[J].膜科学与技术,2017,37(4):33-37.LI X X,ZHANG Z Z,DANG J,et al.Modification of poly(vinylidene fluoride)porous membranes by surface coating with poly(vinyl alcohol)on the basis of factorial design[J].Membrane Science and Technology,2017,37(4):33-37(in Chinese).
[20]史新洋.不对称静电场耦合气体分离过程[D].天津:天津工业大学,2014.SHI X Y.Membrane gas dehydration in a pressure-electric coupled field[D].Tianjin:Tianjin Polytechnic University,2014(in Chinese).