Preparation of polysulfone-based block copolymer ultrafiltration membranes by selective swelling and sacrificing nanofillers

Abstract

Selective swelling of block copolymers of polysulfone-b-poly(ethylene glycol) is an emerging strategy to prepare new types of polysulfone ultrafiltration membranes. Herein, we prepared nanoporous polysulfone-b-poly(ethylene glycol) ultrafiltration membranes by selective swelling and further promoted their porosity and ultrafiltration performances by using CaCO₃ nanoparticles as the sacrificial nanofillers. Different contents of CaCO₃ nanoparticles were doped into the solution of polysulfone-b-poly(ethylene glycol), and thus obtained suspensions were used to prepare both self-supported and bi-layered composite structures. Selective swelling was performed on the obtained block copolymer structures in the solvent pair of ethanol/acetone, producing nanoporous membranes with poly(ethylene glycol) lined along pore walls. The CaCO₃ nanoparticles dispersed in polysulfone-b-poly(ethylene glycol) were subsequently etched away by hydrochloric acid and the spaces initially occupied by CaCO₃ provided extra pores to the block copolymer layers. The porosity of the membranes was increased with increasing CaCO₃ content up to 41%, but further increase in the CaCO₃ content led to partial collapse of the membrane. The sacrificial CaCO₃ particles provided extra pores and enhanced the connectivity between adjacent pores. Consequently, the membranes prepared under optimized conditions exhibited up to 80% increase in water permeance with slight decrease in rejection compared to neat membranes without the use of sacrificial CaCO₃ particles.

Graphical abstract

Keywords

block copolymers / selective swelling / ultrafiltration / CaCO₃ nanoparticles / sacrificial nanofillers

References

[1] Amanda A, Kulprathipanja A, Toennesen M, Mallapragada S K. Semicrystalline poly(vinyl alcohol) ultrafiltrationmembranes for bioseparations. Journal of Membrane Science, 2000, 176(1): 87–95

[2] Lee A, Elam J W, Darling S B. Membrane materials for water purification: design, development, and application. Environmental Science. Water Research & Technology, 2016, 2(1): 17–42

[3] Castro-Muñoz R, Boczkaj G, Gontarek E, Cassano A, Fíla V. Membrane technologies assisting plant-based and agro-food by-products processing: a comprehensive review. Trends in Food Science & Technology, 2020, 95: 219–232

[4] Boulkrinat A, Bouzerara F, Harabi A, Harrouche K, Stelitano S, Russo F, Galiano F, Figoli A. Synthesis and characterization of ultrafiltration ceramic membranes used in the separation of macromolecular proteins. Journal of the European Ceramic Society, 2020, 40(15): 5967–5973

[5] Premnath S, Agarwal G P. Single stage ultrafiltration for enhanced reverse selectivity in a binary protein system. Separation Science and Technology, 2017, 52(13): 2161–2172

[6] Park J Y, Acar M H, Akthakul A, Kuhlman W, Mayes A M. Polysulfone-graft-poly(ethylene glycol) graft copolymers for surface modification of polysulfone membranes. Biomaterials, 2006, 27(6): 856–865

[7] Yang Y N, Zhang H X, Wang P, Zheng Q Z, Li J. The influence of nano-sized TiO₂ fillers on the morphologies and properties of PSF UF membrane. Journal of Membrane Science, 2007, 288(1-2): 231–238

[8] Zodrow K, Brunet L, Mahendra S, Li D, Zhang A, Li Q L, Alvarez P J J. Polysulfone ultrafiltration membranes impregnated with silver nanoparticles show improved biofouling resistance and virus removal. Water Research, 2009, 43(3): 715–723

[9] Rana D, Matsuura T. Surface modifications for antifouling membranes. Chemical Reviews, 2010, 110(4): 2448–2471

[10] Sheldon J M, Reed I M, Hawes C R. The fine-structure of ultrafiltration membranes. 2. Protein fouled membranes. Journal of Membrane Science, 1991, 62(1): 87–102

[11] Mauter M S, Wang Y, Okemgbo K C, Chinedum O O, Giannelis E P, Elimelech M. Antifouling ultrafiltration membranes via post-fabrication grafting of biocidal nanomaterials. ACS Applied Materials & Interfaces, 2011, 3(8): 2861–2868

[12] Chen Y Q, Wei M J, Wang Y. Upgrading polysulfone ultrafiltration membranes by blending with amphiphilic block copolymers: beyond surface segregation. Journal of Membrane Science, 2016, 505: 53–60

[13] Wang N, Wang T, Hu Y X. Tailoring membrane surface properties and ultrafiltration performances via the self-assembly of polyethylene glycol-block-polysulfone-block-polyethylene glycol block copolymer upon thermal and solvent annealing. ACS Applied Materials & Interfaces, 2017, 9(36): 31018–31030

[14] Wang Z G, Yao X P, Wang Y. Swelling-induced mesoporous block copolymer membranes with intrinsically active surfaces for size-selective separation. Journal of Materials Chemistry, 2012, 22(38): 20542–20548

[15] Guo L M, Wang Z G, Wang Y. Selective swelling of block copolymers for porous nanostructures. World Scientific Reference of Hybrid Materials, 2018, 1(15): 45–118

[16] Zhao W, Su Y L, Li C, Shi Q, Ning X, Jiang Z Y. Fabrication of antifouling polyethersulfone ultrafiltration membranes using Pluronic F127 as both surface modifier and pore-forming agent. Journal of Membrane Science, 2008, 318(1-2): 405–412

[17] Wang S F, Feng J Y, Xie Y, Tian Z Z, Peng D D, Wu H, Jiang Z Y. Constructing asymmetric membranes via surface segregation for efficient carbon capture. Journal of Membrane Science, 2016, 500: 25–32

[18] Zhao Y F, Zhang P B, Sun J, Liu C J, Zhu L P, Xu Y Y. Electrolyte-responsive polyethersulfone membranes with zwitterionic polyethersulfone-based copolymers as additive. Journal of Membrane Science, 2016, 510: 306–313

[19] Hancock L F, Fagan S M, Ziolo M S. Hydrophilic, semipermeable membranes fabricated with poly(ethylene oxide)-polysulfone block copolymer. Biomaterials, 2000, 21(7): 725–733

[20] Du R K, Gao B J, Li Y B. Hydrophilic polysulfone film prepared from polyethylene glycol monomethylether via coupling graft. Applied Surface Science, 2013, 274: 288–294

[21] Wang Y. Nondestructive creation of ordered nanopores by selective swelling of block copolymers: toward homoporous membranes. Accounts of Chemical Research, 2016, 49(7): 1401–1408

[22] Yan N N, Wang Y. Selective swelling induced pore generation of amphiphilic block copolymers: the role of swelling agents. Journal of Polymer Science. Part B, Polymer Physics, 2016, 54(9): 926–933

[23] Wang Y, Li F B. An emerging pore-making strategy: confined swelling-induced pore generation in block copolymer materials. Advanced Materials, 2011, 23(19): 2134–2148

[24] Shar J A, Obey T M, Cosgrove T. Adsorption studies of polyethers. Part 1. Adsorption onto hydrophobic surfaces. Colloids and Surfaces. A, Physicochemical and Engineering Aspects, 1998, 136(1-2): 21–33

[25] Zhou J M, Wang Y. Selective swelling of block copolymers: an upscalable greener process to ultrafiltration membranes? Macromolecules, 2020, 53(1): 5–17

[26] Yang H, Zhou J M, Wang Z G, Shi X S, Wang Y. Selective swelling of polysulfone/poly(ethylene glycol) block copolymer towards fouling-resistant ultrafiltration membranes. Chinese Journal of Chemical Engineering, 2020, 28(1): 98–103

[27] Arthanareeswaran G, Sriyamuna Devi T K, Raajenthiren M. Effect of silica particles on cellulose acetate blend ultrafiltration membranes: Part I. Separation and Purification Technology, 2008, 64(1): 38–47

[28] Emadzadeh D, Lau W J, Matsuura T, Ismail A F, Rahbari-Sisakht M. Synthesis and characterization of thin film nanocomposite forward osmosis membrane with hydrophilic nanocomposite support to reduce internal concentration polarization. Journal of Membrane Science, 2014, 449: 74–85

[29] Emadzadeh D, Lau W J, Matsuura T, Rahbari-Sisakht M, Ismail A F. A novel thin film composite forward osmosis membrane prepared from PSf-TiO₂ nanocomposite substrate for water desalination. Chemical Engineering Journal, 2014, 237: 70–80

[30] Ma N, Wei J, Qi S, Zhao Y, Gao Y B, Tang C Y Y. Nanocomposite substrates for controlling internal concentration polarization in forward osmosis membranes. Journal of Membrane Science, 2013, 441: 54–62

[31] Lai L L, Shao J, Ge Q Q, Wang Z B, Yan Y S. The preparation of zeolite NaA membranes on the inner surface of hollow fiber supports. Journal of Membrane Science, 2012, 409–410: 318–328

[32] Vilakati G D, Wong M C Y, Hoek E M V, Mamba B B. Relating thin film composite membrane performance to support membrane morphology fabricated using lignin additive. Journal of Membrane Science, 2014, 469: 216–224

[33] Deng C, Zhang Q G, Han G L, Gong Y, Zhu A M, Liu Q L. Ultrathin self-assembled anionic polymer membranes for superfast size-selective separation. Nanoscale, 2013, 5(22): 11028–11034

[34] Liu H Y, Liu L L, Yang C L, Li Z H, Xiao Q Z, Lei G T, Ding Y H. A hard-template process to prepare three-dimensionally macroporous polymer electrolyte for lithium-ion batteries. Electrochimica Acta, 2014, 121: 328–336

[35] Uchida E, Uyama Y, Ikada Y. Zeta potential of polycation layers grafted onto a film surface. Langmuir, 1994, 10(4): 1193–1198

[36] Wang Z G, Liu R, Yang H, Wang Y. Nanoporous polysulfones with in situ PEGylated surfaces by a simple swelling strategy using paired solvents. Chemical Communications, 2017, 53(65): 9105–9108

[37] Darling S B. Directing the self-assembly of block copolymers. Progress in Polymer Science, 2007, 32(10): 1152–1204

[38] Abetz V, Simon P F W. Phase behaviour and morphologies of block copolymers. Advances in Polymer Science, 2005, 189: 125–212

[39] Aimar P, Meireles M, Sanchez V. A contribution to the translation of retention curves into pore size distributions for sieving membranes. Journal of Membrane Science, 1990, 54(3): 321–338

[40] Calvo J I, Peinador R I, Prádanos P, Palacio L, Bottino A, Capannelli G, Hernández A. Liquid–liquid displacement porometry to estimate the molecular weight cut-off of ultrafiltration membranes. Desalination, 2011, 268(1-3): 174–181

Acknowledgements

Financial support from the National Natural Science Foundations of China (Grant Nos. 21776126 and 21825803) are gratefully acknowledged. We also thank the support from the Program of Excellent Innovation Teams of Jiangsu Higher Education Institutions and the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-021-2038-x and is accessible for authorized users.

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