A Review on Preparation of Microporous Polymeric Membranes Based on Non-solvent Induced Phase Separation

PENG Wan-xin; ZHANG Dao-xin; YANG Feng; CAO Ya; XIANG Ming; WU Tong

doi:10.14028/j.cnki.1003-3726.2024.24.164

您当前的位置：

首页 >

文章列表页 >

A Review on Preparation of Microporous Polymeric Membranes Based on Non-solvent Induced Phase Separation

Special Topic: Polymer Functional Membrances | 更新时间：2025-03-28

- A Review on Preparation of Microporous Polymeric Membranes Based on Non-solvent Induced Phase Separation
- Polymer Bulletin Vol. 38, Issue 4, Pages: 525-534(2025)
- 作者机构：
  
  四川大学高分子材料工程国家重点实验室，成都 610065
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2024.24.164
  CLC：
- Received：30 May 2024，
  
  Accepted：04 July 2024，
  
  Published Online：08 August 2024，
  
  Published：20 April 2025
- 稿件说明：
移动端阅览
彭琬馨, 张道鑫, 杨锋, 曹亚, 向明, 吴桐. 基于非溶剂诱导相分离原理制备聚合物微孔膜的研究进展. 高分子通报, 2025, 38(4), 525–534.

Peng, W. X.; Zhang, D. X.; Yang, F.; Cao, Y.; Xiang, M.; Wu, T. A review on preparation of microporous polymeric membranes based on non-solvent induced phase separation. Polym. Bull. (in Chinese), 2025, 38(4), 525–534.
彭琬馨, 张道鑫, 杨锋, 曹亚, 向明, 吴桐. 基于非溶剂诱导相分离原理制备聚合物微孔膜的研究进展. 高分子通报, 2025, 38(4), 525–534. DOI： 10.14028/j.cnki.1003-3726.2024.24.164.

Peng, W. X.; Zhang, D. X.; Yang, F.; Cao, Y.; Xiang, M.; Wu, T. A review on preparation of microporous polymeric membranes based on non-solvent induced phase separation. Polym. Bull. (in Chinese), 2025, 38(4), 525–534. DOI： 10.14028/j.cnki.1003-3726.2024.24.164.

摘要

非溶剂诱导相分离法是工业制备聚合物微孔膜的最常用方法，具有操作简单、微孔结构可控等多种优势。在非溶剂诱导相分离过程中，相分离行为直接决定微孔膜的微孔结构与使用性能，因此相分离过程成膜机理的研究对微孔膜的生产加工与应用具有重大意义。本文介绍了非溶剂诱导相分离法的成型原理以及相分离过程中热力学驱动力和动力学能垒对其微孔结构的影响研究进展，对高性能聚合物微孔膜的制备与应用提供理论指导。

Abstract

Non-solvent induced phase separation is the most common method for the industrial fabrication of microporous polymeric membranes due to its ease of operation and adjustable microporous structure. During non-solvent induced phase separation process

the phase separation behavior directly determines the microporous structure and performance of the membrane

therefore the research of phase separation mechanism is of paramount significance for the fabrication and application of microporous membranes. This review introduces membrane formation mechanism of non-solvent induced phase separation

and the research progress on the impact of thermodynamic driving force and kinetic barrier on the microporous structure

providing theoretical support for the fabrication and application of high-performance microporous polymeric membranes.

关键词

Keywords

references

Venault, A. ; Chang, Y. ; Wang, D. M. ; Bouyer, D . A review on polymeric membranes and hydrogels prepared by vapor-induced phase separation process . Polym. Rev. , 2013 , 53 ( 4 ), 568 – 626 .

Wu, T. ; Wang, K. ; Chen, X. ; Yang, X. ; Xiang, M. ; Fu, Q . Practicing the concept of “structuring” processing in the manufacture of polymer films . Sci. China Chem. , 2023 , 66 ( 4 ), 993 – 1010 .

罗本喆 , 张军 , 王晓林 . 热致相分离法制备聚烯烃微孔膜研究进展 . 高分子通报 , 2005 , 18 ( 3 ), 40 – 46 .

Ismail, N. ; Venault, A. ; Mikkola, J. P. ; Bouyer, D. ; Drioli, E. ; Tavajohi Hassan Kiadeh, N . Investigating the potential of membranes formed by the vapor induced phase separation process . J. Membr. Sci. , 2020 , 597 .

Yip, Y. ; McHugh, A. J . Modeling and simulation of nonsolvent vapor-induced phase separation . J. Membr. Sci. , 2006 , 271 ( 1-2 ), 163 – 176 .

Khare, V. ; Greenberg, A. ; Krantz, W . Vapor-induced phase separation—effect of the humid air exposure step on membrane morphology. Part I. Insights from mathematical modeling . J. Membr. Sci. , 2005 , 258 ( 1-2 ), 140 – 156 .

Bouyer, D. ; Werapun, W. ; Pochat-Bohatier, C. ; Deratani, A . Morphological properties of membranes fabricated by VIPS process using PEI/NMP/water system: SEM analysis and mass transfer modelling . J. Membr. Sci. , 2010 , 349 ( 1 ), 97 – 112 .

Peng, W. ; Li, Z. ; Peng, X. ; Yang, F. ; Cao, Y. ; Xiang, M. ; Wu, T . Formation mechanism of ordered porous nitrocellulose membranes by breath figure templating . Polymer , 2024 , 294 .

Loeb, S. ; Sourirajan, S . Sea water demineralization by means of an osmotic membrane. In saline water conversion—II . Adv. Chem. Ser. , 1963 , 117 – 132 .

Bawn, C. ; Wajid, M . High polymer solutions. Part 7. Vapour pressure of polystyrene solutions in acetone, chloroform and propyl acetate . Trans. Faraday Society. , 1956 , 52 , 1658 – 1664 .

Strathmann, H. ; Kock, K . The formation mechanism of phase inversion membranes . Desalination , 1977 , 21 ( 3 ), 241 – 255 .

Strathmann, H. ; Scheible, P. ; Baker, R . A rationale for the preparation of Loeb‐Sourirajan‐type cellulose acetate membranes . J. Appl. Polym. Sci. , 1971 , 15 ( 4 ), 811 – 828 .

Altena, F. W. ; Smolders, C . Calculation of liquid-liquid phase separation in a ternary system of a polymer in a mixture of a solvent and a nonsolvent . Macromolecules, 1982 , 15 ( 6 ), 1491 – 1497 .

Yilmaz, L. ; McHugh, A . Analysis of nonsolvent-solvent-polymer phase diagrams and their relevance to membrane formation modeling . J. Appl. Polym. Sci. , 1986 , 31 ( 4 ), 997 – 1018 .

Tompa, P. S . Polymer Solutions . London : Butterworths Scientific Publications , 1956 , 43 .

李学 , 韩艳春 , 安立佳 , 王喆 . 高分子混合物薄膜的相分离行为 . 高分子通报 , 2002 , ( 2 ), 11 .

Peng, N. ; Chung, T. S. ; Chng, M. L. ; Aw, W . Evolution of ultra-thin dense-selective layer from single-layer to dual-layer hollow fibers using novel Extem® polyetherimide for gas separation . J. Membr. Sci. , 2010 , 360 ( 1-2 ), 48 – 57 .

Ulbricht, M. ; Schuster, O. ; Ansorge, W. ; Ruetering, M. ; Steiger, P . Influence of the strongly anisotropic cross-section morphology of a novel polyethersulfone microfiltration membrane on filtration performance . Sep. Purif. Technol. , 2007 , 57 ( 1 ), 63 – 73 .

Albrecht, W. ; Kneifel, K. ; Weigel, T. ; Hilke, R. ; Just, R. ; Schossig, M. ; Ebert, K. ; Lendlein, A . Preparation of highly asymmetric hollow fiber membranes from poly(ether imide) by a modified dry-wet phase inversion technique using a triple spinneret . J. Membr. Sci. , 2005 , 262 ( 1-2 ), 69 – 80 .

Lee, K. W. ; Seo, B. K. ; Nam, S. T. ; Han, M. J . Trade-off between thermodynamic enhancement and kinetic hindrance during phase inversion in the preparation of polysulfone membranes . Desalination , 2003 , 159 ( 3 ), 289 – 296 .

Xu, J. ; Tang, Y. ; Wang, Y. ; Shan, B. ; Yu, L. ; Gao, C . Effect of coagulation bath conditions on the morphology and performance of PSf membrane blended with a capsaicin-mimic copolymer . J. Membr. Sci. , 2014 , 455 , 121 – 130 .

Sadrzadeh, M. ; Bhattacharjee, S . Rational design of phase inversion membranes by tailoring thermodynamics and kinetics of casting solution using polymer additives . J. Membr. Sci. , 2013 , 441 , 31 – 44 .

Lee, H. J. ; Jung, B. ; Kang, Y. S. ; Lee, H . Phase separation of polymer casting solution by nonsolvent vapor . J. Membr. Sci. , 2004 , 245 ( 1-2 ), 103 – 112 .

Park, H. C. ; Kim, Y. P. ; Kim, H. Y. ; Kang, Y. S . Membrane formation by water vapor induced phase inversion . J. Membr. Sci. , 1999 , 156 ( 2 ), 169 – 178 .

Tree, D. R. ; Iwama, T. ; Delaney, K. T. ; Lee, J. ; Fredrickson, G. H . Marangoni flows during nonsolvent induced phase separation . ACS Macro Lett. , 2018 , 7 ( 5 ), 582 – 586 .

Garcia, J. U. ; Iwama, T. ; Chan, E. Y. ; Tree, D. R. ; Delaney, K. T. ; Fredrickson, G. H . Mechanisms of asymmetric membrane formation in nonsolvent-induced phase separation . ACS Macro Lett. , 2020 , 9 ( 11 ), 1617 – 1624 .

Su, Y. S. ; Kuo, C. Y. ; Wang, D. M. ; Lai, J. Y. ; Deratani, A. ; Pochat, C. ; Bouyer, D . Interplay of mass transfer, phase separation, and membrane morphology in vapor-induced phase separation . J. Membr. Sci. , 2009 , 338 ( 1-2 ), 17 – 28 .

Muller, M. ; Abetz, V . Nonequilibrium processes in polymer membrane formation: theory and experiment . Chem. Rev. , 2021 , 121 ( 22 ), 14189 – 14231 .

Suk, D. E. ; Matsuura, T. ; Park, H. B. ; Lee, Y. M . Development of novel surface modified phase inversion membranes having hydrophobic surface-modifying macromolecule (nSMM) for vacuum membrane distillation . Desalination , 2010 , 261 ( 3 ), 300 – 312 .

Radovanovic, P. ; Thiel, S. W. ; Hwang, S. T . Formation of asymmetric polysulfone membranes by immersion precipitation. Part I. Modelling mass transport during gelation . J. Membr. Sci. , 1992 , 65 ( 3 ), 213 – 229 .

Alexowsky, C. ; Bojarska, M. ; Ulbricht, M . Porous poly(vinylidene fluoride) membranes with tailored properties by fast and scalable non-solvent vapor induced phase separation . J. Membr. Sci. , 2019 , 577 , 69 – 78 .

Mohammadi, T. ; Saljoughi, E . Effect of production conditions on morphology and permeability of asymmetric cellulose acetate membranes . Desalination, 2009 , 243 ( 1 ), 1 – 7 .

Altinkaya, S. A. ; Yenal, H. ; Ozbas, B . Membrane formation by dry-cast process model validation through morphological studies . J. Membr. Sci. , 2005 , 249 ( 1-2 ), 163 – 172 .

Radjabian, M. ; Abetz, C. ; Fischer, B. ; Meyer, A. ; Abetz, V . Influence of solvent on the structure of an amphiphilic block copolymer in solution and in formation of an integral asymmetric membrane . ACS Appl. Mater. Interfaces , 2017 , 9 ( 37 ), 31224 – 31234 .

Chuang, W. Y. ; Young, T. H. ; Chiu, W. Y. ; Lin, C. Y . The effect of polymeric additives on the structure and permeability of poly(vinyl alcohol) asymmetric membranes . Polymer , 2000 , 41 ( 15 ), 5633 – 5641 .

Lee, H. J. ; Won, J. ; Lee, H. ; Kang, Y. S . Solution properties of poly(amic acid)–NMP containing LiCl and their effects on membrane morphologies . J. Membr. Sci. , 2002 , 196 ( 2 ), 267 – 277 .

Wang, D. ; Li, K. ; Teo, W . Porous PVDF asymmetric hollow fiber membranes prepared with the use of small molecular additives . J. Membr. Sci. , 2000 , 178 ( 1-2 ), 13 – 23 .

Arthanareeswaran, G. ; Thanikaivelan, P. ; Raguime, J. A. ; Raajenthiren, M. ; Mohan, D . Metal ion separation and protein removal from aqueous solutions using modified cellulose acetate membranes: role of polymeric additives . Sep. Purif. Technol. , 2007 , 55 ( 1 ), 8 – 15 .

Fontananova, E. ; Jansen, J. C. ; Cristiano, A. ; Curcio, E. ; Drioli, E . Effect of additives in the casting solution on the formation of PVDF membranes . Desalination , 2006 , 192 ( 1 ), 190 – 197 .

Mohsenpour, S. ; Esmaeilzadeh, F. ; Safekordi, A. ; Tavakolmoghadam, M. ; Rekabdar, F. ; Hemmati, M . The role of thermodynamic parameter on membrane morphology based on phase diagram . J. Mol. Liq. , 2016 , 224 , 776 – 785 .

Foroutani, K. ; Ghasemi, S. M. ; Pourabbas, B . Molecular tailoring of polystyrene-block-poly(acrylic acid) block copolymer toward additive-free asymmetric isoporous membranes via SNIPS . J. Membr. Sci. , 2021 , 623 , 119099 .

Foroutani, K. ; Ghasemi, S. M. ; Pourabbas, B . Ordered isoporous membranes from ionic diblock copolymers via SNIPS: optimizing effective factors with a structural survey . Prog. Org. Coat. , 2021 , 161 , 106554 .

Menut, P. ; Su, Y. S. ; Chinpa, W. ; Pochat-Bohatier, C. ; Deratani, A. ; Wang, D. M. ; Huguet, P. ; Kuo, C. Y. ; Lai, J. Y. ; Dupuy, C . A top surface liquid layer during membrane formation using vapor-induced phase separation (VIPS)—evidence and mechanism of formation . J. Membr. Sci. , 2008 , 310 ( 1-2 ), 278 – 288 .

Tsai, J. T. ; Su, Y. S. ; Wang, D. M. ; Kuo, J. L. ; Lai, J. Y. ; Deratani, A . Retainment of pore connectivity in membranes prepared with vapor-induced phase separation . J. Membr. Sci. , 2010 , 362 ( 1-2 ), 360 – 373 .

Zsigmondy, R. ; Bachmann, W . Über neue Filter . Z. Anorg.Allg. Chem. , 1918 , 103 , 119 – 128 .

Kim, I. C. ; Lee, K. H. ; Tak, T. M . Preparation and characterization of integrally skinned uncharged polyetherimide asymmetric nanofiltration membrane . J. Membr. Sci. , 2001 , 183 ( 2 ), 235 – 247 .

Alkhudhiri, A. ; Darwish, N. ; Hilal, N . Membrane distillation: a comprehensive review . Desalination , 2012 , 287 , 2 – 18 .

Kang, G. D. ; Cao, Y. M . Application and modification of poly(vinylidene fluoride) (PVDF) membranes—a review . J. Membr. Sci. , 2014 , 463 , 145 – 165 .

Wu, F. ; Xu, Z. ; Wang, Z. ; Shi, Y. ; Li, L. ; Zhang, Z . Membrane-based air separation for catalytic oxidation of isolongifolene . Chem. Eng. J. , 2010 , 158 ( 3 ), 426 – 430 .

Bouyer, D. ; Vachoud, L. ; Chakrabandhu, Y. ; Pochat-Bohatier, C . Influence of mass transfer on gelation time using VIPS-gelation process for chitin dissolved in LiCl/NMP solvent—modelling and experimental study . Chem. Eng. J. , 2010 , 157 ( 2-3 ), 605 – 619 .

Wang, D. M. ; Wu, T. T. ; Lin, F. C. ; Hou, J. Y. ; Lai, J. Y . A novel method for controlling the surface morphology of polymeric membranes . J. Membr. Sci. , 2000 , 169 ( 1 ), 39 – 51 .

Ma, D. ; McHugh, A. J . The interplay of phase inversion and membrane formation in the drug release characteristics of a membrane-based delivery system . J. Membr. Sci. , 2007 , 298 ( 1-2 ), 156 – 168 .

Sun, H. ; Liu, S. ; Ge, B. ; Xing, L. ; Chen, H . Cellulose nitrate membrane formation via phase separation induced by penetration of nonsolvent from vapor phase . J. Membr. Sci. , 2007 , 295 ( 1 ), 2 – 10 .

Zhao, Q. ; Xie, R. ; Luo, F. ; Faraj, Y. ; Liu, Z. ; Ju, X. J. ; Wang, W. ; Chu, L. Y . Preparation of high strength poly(vinylidene fluoride) porous membranes with cellular structure via vapor-induced phase separation . J. Membr. Sci. , 2018 , 549 , 151 – 164 .

Ye, Q. ; Cheng, L. ; Zhang, L. ; Xing, L. ; Chen, H . Preparation of symmetric network PVDF membranes for protein adsorption via vapor-induced phase separation . J. Macromol. Sci. B , 2011 , 50 ( 10 ), 2004 – 2022 .

Pinnau, I. ; Wind, J. ; Peinemann, K. V . Ultrathin multicomponent poly(ether sulfone) membranes for gas separation made by dry/wet phase inversion . Ind. Eng. Chem. Res. , 1990 , 29 ( 10 ), 2028 – 2032 .

Chen, Z. ; Deng, M. ; Chen, Y. ; He, G. ; Wu, M. ; Wang, J . Preparation and performance of cellulose acetate/polyethyleneimine blend microfiltration membranes and their applications . J. Membr. Sci. , 2004 , 235 ( 1-2 ), 73 – 86 .

Peng, Y. ; Fan, H. ; Dong, Y. ; Song, Y. ; Han, H . Effects of exposure time on variations in the structure and hydrophobicity of polyvinylidene fluoride membranes prepared via vapor-induced phase separation . Appl. Surf. Sci. , 2012 , 258 ( 20 ), 7872 – 7881 .

Li, C. L. ; Wang, D. M. ; Deratani, A. ; Quémener, D. ; Bouyer, D. ; Lai, J. Y . Insight into the preparation of poly(vinylidene fluoride) membranes by vapor-induced phase separation . J. Membr. Sci. , 2010 , 361 ( 1-2 ), 154 – 166 .

Matsuyama, H. ; Teramoto, M. ; Nakatani, R. ; Maki, T . Membrane formation via phase separation induced by penetration of nonsolvent from vapor phase. I. Phase diagram and mass transfer process . J. Appl. Polym. Sci. , 1999 , 74 ( 1 ), 159 – 170 .

Bearman, R. J . Statistical mechanical theory of the diffusion coefficients in binary liquid solutions . J. Chem. Phys. , 1960 , 32 ( 5 ), 1308 – 1313 .

Vrentas, J. ; Duda, J . Diffusion of large penetrant molecules in amorphous polymers . J. Polym. Sci. Polym. Phys. , 1979 , 17 ( 6 ), 1085 – 1096 .

Sacide Alsoy, A. ; Ozbas, B . Modeling of asymmetric membrane formation by dry-casting method . J. Membr. Sci. , 2004 , 230 ( 1-2 ), 71 – 89 .

Montembault, A. ; Viton, C. ; Domard, A . Rheometric study of the gelation of chitosan in aqueous solution without cross-linking agent . Biomacromolecules , 2005 , 6 ( 2 ), 653 – 662 .

Venault, A. ; Bouyer, D. ; Pochat‐Bohatier, C. ; Vachoud, L. ; Faur, C . Investigation of chitosan gelation mechanisms by a modeling approach coupled to local experimental measurement . AIChE J. , 2012 , 58 ( 7 ), 2226 – 2240 .

Shojaie, S. S. ; Krantz, W. B. ; Greenberg, A. R . Dense polymer film and membrane formation via the dry-cast process part I. Model development . J. Membr. Sci. , 1994 , 94 ( 1 ), 255 – 280 .

张学芳 ; 胡晓宇 ; 肖长发 . 聚合物分离膜成形过程中相分离数值模拟研究进展 . 高分子通报 , 2011 , 24 ( 2 ), 64 – 72 .

Jansen, J. C. ; Buonomenna, M. G. ; Figoli, A. ; Drioli, E . Asymmetric membranes of modified poly(ether ether ketone) with an ultra-thin skin for gas and vapour separations . J. Membr. Sci. , 2006 , 272 ( 1-2 ), 188 – 197 .

Krantz, W. B. ; Greenberg, A. R. ; Hellman, D. J . Dry-casting: Computer simulation, sensitivity analysis, experimental and phenomenological model studies . J. Membr. Sci. , 2010 , 354 ( 1-2 ), 178 – 188 .

Al Ansari, Z. ; Vega, L. F. ; Zou, L . Emulsified oil fouling resistant cellulose acetate-MoS 2 -nanocomposite membrane for oily wastewater remediation . Desali-nation , 2024 , 575 .

Mandal, J. ; Fu, Y. ; Overvig, A. C. ; Jia, M. ; Sun, K. ; Shi, N. N. ; Zhou, H. ; Xiao, X. ; Yu, N. ; Yang, Y . Hierarchically porous polymer coatings for highly efficient passive daytime radiative cooling . Science , 2018 , 362 ( 6412 ), 315 – 319 .

Kesting, R . Concerning the microstructure of dry‐RO membranes . J. Appl. Polym. Sci. , 1973 , 17 ( 6 ), 1771 – 1785 .

Pervin, R. ; Ghosh, P. ; Basavaraj, M. G . Tailoring pore distribution in polymer films via evaporation induced phase separation . RSC Adv. , 2019 , 9 ( 27 ), 15593 – 15605 .

Ghasemi, S. M. ; Kholghi, A . Porous films prepared from poly(styrene- co -acrylonitrile)/dichloromethane system via evaporation induced phase separation: structure- thermodynamic aspects . Prog. Org. Coat. , 2022 , 168 .

Tsay, C. ; McHugh, A . Mass transfer dynamics of the evaporation step in membrane formation by phase inversion . J. Membr. Sci. , 1991 , 64 ( 1-2 ), 81 – 92 .

Phong, H. Q. ; Wang, S. L. ; Wang, M. J . Cell behaviors on micro-patterned porous thin films . Mater. Sci. Eng., B , 2010 , 169 ( 1-3 ), 94 – 100 .

Wang, Y. ; Liu, Z. ; Huang, Y. ; Han, B. ; Yang, G . Micropatterned polymer surfaces induced by nonsolvent . Langmuir , 2006 , 22 ( 4 ), 1928 – 1931 .

Honarbakhsh, S. ; Pourdeyhimi, B . Scaffolds for drug delivery, part I: electrospun porous poly(lactic acid) and poly(lactic acid)/poly(ethylene oxide) hybrid scaffolds . J. Membr. Sci. , 2010 , 46 ( 9 ), 2874 – 2881 .

Views

4016

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

No data

Related Author

No data

Related Institution

No data

⁰