Special lssues

Progress in the preparation and application of thermo- and pH-responsive polymer membranes

  • JIANG Ping ,
  • WU Yiqiang
  • School of Materials Science and Engineering, Central South University of Forestry and Technology, Changsha 410004, China

Received date: 2015-12-15

  Revised date: 2016-06-30

  Online published: 2016-10-21


The environmental responsive intelligent polymer membrane has broad prospects in the fields of material separation, control and release. In this paper, the preparation methods and applications of the thermo- and pH-responsive polymer membranes are reviewed, and the construction method, the structure activity relationship and the response mechanism of the non-polar and self-support thermo- and pH-responsive polymers are discussed.

Cite this article

JIANG Ping , WU Yiqiang . Progress in the preparation and application of thermo- and pH-responsive polymer membranes[J]. Science & Technology Review, 2016 , 34(19) : 22 -30 . DOI: 10.3981/j.issn.1000-7857.2016.19.002


[1] Schmaljohann D.Thermo-and pH-responsive polymers in drug delivery[J].Advanced Drug Delivery Reviews,2006,58(15):1655-1670.
[2] Lokuge I,Wang X J,Bohn P W.Temperature-controlled flow switching in nanocapillary array membranes mediated by poly(N-isopropylacryl-amide) polymer brushes grafted by atom transfer radical polymerization[J].Langmuir,2007,23(1):305-311.
[3] Nakayama H,Kaetsu I,Uchida K,et al.Preparation of temperature re-sponsive fragrance release membranes by UV curing[J].Radiation Phys-ics and Chemistry,2003,67(2):131-136.
[4] Zhang K,Wu X Y.Temperature and pH-responsive polymeric compos-ite membranes for controlled delivery of proteins and peptides[J].Bioma-terials,2004,25(22):5281-5291.
[5] Yang B,Yang W T.Thermo-Sensitive switching membranes regulated by pore-covering polymer brushes[J].Journal of Membrane Science,2003,218(1-2):247-255.
[6] Xie R,Li Y,Chu L Y.Preparation of thermo-responsive gating mem-branes with controllable response temperature[J].Journal of Membrane Science,2007,289(1-2):76-85.
[7] Zhao C S,Nie S Q,Tang M,et al.Polymeric pH-sensitive membranesA review[J].Progress in Polymer Science,2011,36(11):1499-1520.
[8] Ito Y,Ochiai Y,Park Y S,et al.pH-sensitive Gating by conformational change of a polypeptide brush grafted onto a porous polymer membrane[J].Journal of American chemical society,1997,119(7):1619-1623.
[9] Wang D Q,Tan J J,Kang H L,et al.Synthesis,self-assembly and drug release behaviors of pH-responsive copolymers ethyl cellulosegraft-PDEAEMA through ATRP[J].Carbohydrate Polymers,2011,84(1):195-202.
[10] Vladimir T.Multifunctional and stimuli-sensitive pharmaceutical nano-carriers[J].European Journal of Pharmaceutics and Biopharmaceutics,2009,71(3):431-444.
[11] Park H W,Jin H S,Yang S Y,et al.Tunable phase transition behav-iors of pH-sensitive polyaspartamides having various cationic pendant groups[J].Colloid and Polymer Science,2009,287(3):919-926.
[12] Franck-Lacaze L,Sistat P,Huguet P.Determination of the pK(a) of poly(4-vinylpyridine)-based weak anion exchange membranes for the investigation of the side proton leakage[J].Journal of Membrane Sci-ence,2009,326(2):650-658.
[13] M'Bareck C O,Nguyen Q T,Alexandre S,et al.Fabrication of ion-ex-change ultrafiltration membranes for water treatment I.Semi-interpene-trating polymer networks of polysulfone and poly(acrylic acid)[J].Jour-nal of Membrane Science,2006,278(1-2):10-18.
[14] Mbareck C,Nguyen Q T,Alaoui O T,et al.Elaboration,characteriza-tion and application of polysulfone and polyacrylic acid blends as ul-trafiltration membranes for removal of some heavy metals from water[J].Journal of Hazardous Materials,2009,171(1-3):93-101.
[15] Zhang K,Huang H Y,Yang G C,et al.Characterization of nanostruc-ture of stimuli-responsive polymeric composite membranes[J].Biomac-romolecules,2004,5(4):1248-1255.
[16] Hu K,Dickson J M.Development and characterization of poly(vinyli-dene fluoride)-poly(acrylic acid) pore-filled pH-sensitive membranes[J].Journal of Membrane Science,2007,301(1-2):19-28.
[17] Hu K,Dickson J M.Modelling of the pore structure variation with pH for pore-filled pH-sensitive poly(vinylidene fluoride)-poly(acrylic ac-id) membranes[J].Journal of Membrane Science,2008,321(2):162-171.
[18] Abu Seman M N,Khayet M,Bin Ali Z I,et al.Reduction of nanofiltra-tion membrane fouling by UV-initiated graft polymerization technique[J].Journal of Membrane Science,2010,355(1-2):133-141.
[19] Shi Q,Su Y L,Ning X,et al.Graft polymerization of methacrylic acid onto polyethersulfone for potential pH-responsive membrane materials[J].Journal of Membrane Science,2010,347(1-2):62-68.
[20] He D M,Susanto H,Ulbricht M.Photo-irradiation for preparation,modification and stimulation of polymeric membranes[J].Progress in Polymer Science,2009,34(1):62-98.
[21] Li W H,Liu P B,Zou H W,et al.pH sensitive microporous polypro-pylene membrane prepared through ozone induced surface grafting[J].Polymers of Advanced Technologies,2009,20(3):251-257.
[22] Akamatsu K,Yamaguchi T.Novel preparation method for obtaining pH-responsive core-shell microcapsule reactors[J].Industrial & Engi-neering Chemistry Research,2007,46(1):124-130.
[23] Tong G S,Liu T,Zhao L,et al.Supercritical carbon dioxide-assisted preparation of polypropylene grafted acrylic acid with high grafted con-tent and small gel percent[J].The Journal of Supercritical Fluids,2009,48(3):261-268.
[24] Zhou J,Li W,Gu J S,et al.Development of a novel RAFT-UV graft-ing technique to modify polypropylene membrane used for NOM re-moval[J].Separation and Purification Technology,2010,71(2):233-240.
[25] Schepelina O,Poth N,Zharov I.pH-responsive nanoporous silica col-loidal membranes[J].Advanced Functional Materials,2010,20(12):1962-1969.
[26] Wang M,An Q F,Wu L G,et al.Preparation of pH-responsive phe-nolphthalein poly(ether sulfone) membrane by redox-graft pore-filling polymerization technique[J].Journal of Membrane Science,2007,287(2):257-263.
[27] Guo H F,Ulbricht M.Preparation of thermo-responsive polypropylene membranes via surface entrapment of poly(N-isopropylacrylamide)-containing macromolecules[J].Journal of Membrane Science,2011,372(1-2):331-339.
[28] Su M,Teoh M M,Wang K Y,et al.Effeet of inner-layer thermal con-duetivity on flux enhancement of dual-layer hollow fiber membranes in direet contact membrane distillation[J].Journal of Membrane Sci-ence,2010,364:278-289.
[29] 王闻宇.聚偏氟乙烯智能膜的制备及其性能研究[D].天津:天津工业大学,2006.Wang Wenyu.PreParation and ProPerties of Intelligent Poly(vinyli-dene fluoride) Membranes[D].Tianjin:Tianjin Polytechnic University,2006.
[30] Peinemann K V,Abetz V,Simon P F W,Asymmetric superstructure formed in a block copolymer via phase separation[J].Nature Materials,2007,6(12):992-997.
[31] Schacher F,Ulbricht M,Müller A H E.Self-supporting,double stimu-li-responsive porous membranes from polystyrene-block-poly(N,Ndimethylaminoethyl methacrylate) diblock copolymers[J].Advanced Functional Materials,2009,19(7):1040-1045.
[32] Schacher F,Rudolph T,Wieberger F,et al.Double stimuli-responsive ultrafiltration membranes from polystyrene-block poly(N,N-dimethyl-aminoethyl methacrylate) diblock copolymers[J].Applied Materials and Interfaces,2009,1(7):1492-1503.
[33] Du J,Tao C Y,He X,et al.Environmentally sensitive microfiltration membranes with pH responsive valve[J].Journal of Central South Uni-versity of Technology,2007,14(Suppl 3):472-475.
[34] Karppi J,Akerman S,Akerman K,et al.Adsorption of metal cations from aqueous solutions onto the pH responsive poly(vinylidene fluo-ride grafted poly(acrylic acid)(PVDF-PAA) membrane[J].Journal of Polymer Research,2010,17(1):71-76.
[35] Li C Y,Cao B,Wang W C,et al.pH-induced on-off switching of polycarbonate track-etched membranes by plasma-induced surface grafting[J].Polymers for Advanced Technologies,2010,21(10):698-703.
[36] Lue S J,Chen C H,Shih C M,et al.Grafting of poly(N-isopro-pylacrylamide-co-acrylic acid) on micro-porous polycarbonate films:regulating lower critical solution temperatures for drug controlled re-lease[J].Journal of Membrane Science,2011,379(1):330-340.
[37] Guo H,Ulbricht M.Surface modification of polypropylene microfiltra-tion membrane via entrapment of an amphiphilic alkyl oligoethyleneg-lycolether[J].Journal of Membrane Science,2010,349:312-320.
[38] Guo H,Ulbricht M.The effects of(macro) molecular structure on hy-drophilic surface modification of polypropylene membranes via entrap-ment[J].Journal of Colloid and Interface Science,2010,350:99-109.
[39] Berndt E,Ulbricht M.Synthesis of block copolymers for surface func-tionalization with stimuli-responsive macromolecules[J].Polymer,2009,50(22):5181-5191.
[40] Jain S,Bajpai A K.Investigation of water sorption and blood compati-ble behaviors of polyethylene glycol(PEG) plasticized membranes of poly(vinyl alcohol-g-acrylonitrile)[J].Advanced Science,Engineering and Medicine,2012,4(6):469-478.
[41] Franck-Lacaze L,Sistat P,Huguet P.Determination of the pKa of poly(4-vinylpyridine)-based weak anion exchange membranes for the investigation of the side proton leakage[J].Journal of Membrane Science,2009,326(2):650-658.
[42] Du J,Tao C Y,He X,et al.Environmentally sensitive microfiltration membranes with pH responsive valve[J].Journal of Central South Uni-versity of Technology,2007,14(Suppl 3):472-475.
[43] Liu S,Billingham N C,Armes S P.A schizophrenic water-soluble di-block copolymer[J].Angewandte Chemie International Edition,2001,40(12):2328-2331.
[44] Bousquet A,Ibarboure E,Papon E,et al.Structured multistimuli-re-sponsive functional polymer surfaces obtained by interfacial diffusion of amphiphilic block copolymers[J].Journal of Polymer Science Part A:Polymer Chemistry,2010,48(9):1952-1961.
[45] Hou J W,Shi Q,Stagnaro,P.Aqueious-based immobilization of initi-tor and surface-initiated ATRP to construct henriocompatible surface of poly(styrene-b-(ethylene-co-butylene)-b-styrene) elastome[J].Colloids and Surfaces B-Biointerfaces,2013,111:333-341.
[46] Perera D H N,Nataraj S K,Thomson N M,et al.Room-temperature development of thin film composite reverse osmosis membranes from cellulose acetate with antibacterial properties[J].Journal of Membrane Science,2014,453:212-220.