Characterization of temperature-sensitive membranes prepared from poly(vinylidene fluoride)-graft-poly(N-isopropylacrylamide) copolymers obtained by atom transfer radical polymerization

Abstract

In this paper, poly(vinylidene fluoride)-graft-poly(N-isopropylacrylamide) (PVDF-g-PNIPAAm) copolymers were synthesized directly via grafting temperature-sensitive material NIPAAm on PVDF by atom transfer radical polymerization (ATRP). The chemical structure of the graft copolymers was characterized by Fourier transform infrared (FTIR) and ¹H-NMR spectroscopy. The temperature-sensitive membranes were prepared from the PVDF-g-PNIPAAm copolymers by the immersion precipitation process of the phase inversion method. The chemical composition and pore structure of the PVDF-g-PNIPAAm membranes were studied by X-ray photoelectron spectroscopy (XPS) and an automatic mercury porosimeter, respectively. The effects of temperature on pure water flux and bovine serum albumen (BSA) rejection ratio of the membranes were also investigated. The results showed that the grafted PNIPAAm chains tended to enrich on the surfaces of the membranes or the membrane pores during the membrane-forming process. Pore diameter and porosity of the copolymer membranes were larger than those of the pristine PVDF membranes. Also, the PVDF-g-PNIPAAm membranes could exhibit temperature-sensitive performance in water flux and BSA rejection measurements.

Keywords

poly(vinylidene fluoride) (PVDF) / N-isopropylacrylamide (NIPAAm) / atom transfer radical polymerization (ATRP) / temperature-sensitive membrane

References

[1] Liang L, Feng X D, Peurrung L, . Temperature-sensitive membranes prepared by UV photopolymerization of N-isopropylacrylamide on a surface of porous hydrophilic polypropylene membranes. Journal of Membrane Science, 1999, 162(1-2): 235–246

[2] Alem H, Duwez A S, Lussis P, . Microstructure and thermo-responsive behavior of poly(N-isopropylacrylamide) brushes grafted in nanopores of track-etched membranes. Journal of Membrane Science, 2008, 308(1-2): 75–86

[3] Li P F, Xie R, Jiang J C, . Thermo-responsive gating membranes with controllable length and density of poly(N-isopropylacrylamide) chains grafted by ATRP method. Journal of Membrane Science, 2009, 337(1-2): 310–317

[4] Yang W C, Xie R, Pang X Q, . Preparation and characterization of dual stimuli-responsive microcapsules with a superparamagnetic porous membrane and thermo-responsive gates. Journal of Membrane Science, 2008, 321(2): 324–330

[5] Li Y, Chu L Y, Zhu J H, . Thermo-responsive gating characteristics of poly(N-isopropylacrylamide)-grafted porous poly(vinylidene fluoride) membranes. Industrial & Engineering Chemistry Research, 2004, 43(11): 2643–2649

[6] Ying L, Kang E T, Neoh K G. Synthesis and characterization of poly(N-isopropylacrylamide)-graft-poly(vinylidene fluoride) copolymers and temperature-Sensitive Membranes. Langmuir, 2002, 18(16): 6416–6423

[7] Ying L, Kang E T, Neoh K G, . Drug permeation through temperature-sensitive membranes prepared from poly(vinylidene fluoride) with grafted poly(N-isopropylacrylamide) chains. Journal of Membrane Science, 2004, 243(1-2): 253–262

[8] Xu F J, Li J, Yuan S J, . Thermo-responsive porous membranes of controllable porous morphology from triblock copolymers of polycaprolactone and poly(N-isopropylacrylamide) prepared by atom transfer radical polymerization. Biomacromolecules, 2008, 9(1): 331–339

[9] Kim S Y, Kanamori T, Shinbo T. Preparation of Thermal-responsive poly(propylene) membranes grafted with N-isopropylacrylamide by plasma-induced polymerization and their water permeation. Journal of Applied Polymer Science, 2002, 84(6): 1168–1177

[10] Zhang Z B, Zhu X L, Xu F J, . Temperature- and pH-sensitive nylon membranes prepared via consecutive surface-Initiated atom transfer radical graft polymerizations. Journal of Membrane Science, 2009, 342(1-2): 300–306

[11] Zhai G, Kang E T, Neoh K G. Poly(2-vinylpyridine)- and poly(4-vinylpyridine)-graft-poly(vinylidene fluoride) copolymers and their pH-sensitive microfiltration membranes. Journal of Membrane Science, 2003, 217(1-2): 243–259

[12] Hester J F, Olugebefola S C, Mayes A M. Preparation of pH-responsive polymer membranes by self-organization. Journal of Membrane Science, 2002, 208(1-2): 375–388

[13] Okajima S, Yamaguchi T, Sakai Y, . Regulation of cell adhesion using a signal-responsive membrane substrate. Biotechnology and Bioengineering, 2005, 91(2): 237–243

[14] Ito T, Yamaguchi T. Osmotic pressure control in response to a specific ion signal at physiological temperature using a molecular recognition ion gating membrane. Journal of the American Chemical Society, 2004, 126(20): 6202–6203

[15] Ito T, Sato Y, Yamaguchi T, . Response mechanism of a molecular recognition ion gating membrane. Macromolecules, 2004, 37(9): 3407–3414

[16] Dong Y Y, He X L, Chen L, . Effect of AAc-GA content on swelling behaviors of temperature-sensitive PNIPAAm-based hydrogels. Frontiers of Materials Science in China, 2010, 4(1): 84–89

[17] Stile R A, Burghardt W R, Healy E. Synthesis and characterization of injectable poly(N-isopropyl acrylamide)-based hydrogels that support tissue formation in vitro. Macromolecules, 1999, 32(22): 7370–7379

[18] Homberg S, Nasman J H, Sundholm F. Synthesis and properties of sulfonated and crosslinked poly[(vinylidene fluoride)-graft-styrene] membranes. Polymers for Advanced Technologies, 1998, 9(2): 121–127

[19] Chen Y W, Xiao J C, Zhou W H, . Grafting poly(N-isopropyl acrylamide) from poly(vinylidene fluoride) mirofiltration membranes via direct surface-initiated atom transfer radical polymerization and temperature sensitivity. Surface Review and Letters, 2009, 16(1): 111–121

[20] Chiang Y C, Chang Y, Higuchi A, . Sulfobetaine-grafted poly(vinylidene fluoride) ultrafiltration membranes exhibit excellent antifouling property. Journal of Membrane Science, 2009, 339(1-2): 151–159

[21] Hester J F, Banerjee P, Won Y Y, . ATRP of amphiphilic graft copolymers based on PVDF and their use as membrane additives. Macromolecules, 2002, 35(20): 7652–7661

[22] Inceoglu S, Olugebefola S C, Acar M H, . Atom transfer radical polymerization using poly(vinylidene fluoride) as macroinitiator. Designed Monomers and Polymers, 2004, 7(1-2): 181–189

[23] Wang W Y, Chen L. “Smart” membrane materials: preparation and characterization of PVDF-g-PNIPAAm graft copolymer. Journal of Applied Polymer Science, 2007, 104(3): 1482–1486

[24] Chen Y W, Liu D M, Deng Q L, . Atom transfer radical polymerization directly from poly(vinylidene fluoride): surface and antifouling properties. Journal of Polymer Science, Part A: Polymer Chemistry, 2006, 44(11): 3434–3443

[25] Kim Y W, Lee D K, Lee K J, . Single-step synthesis of proton conducting poly(vinylidene fluoride) (PVDF) graft copolymer electrolytes. European Polymer Journal, 2008, 44(3): 932–939

[26] Matyjaszewski K, Xia J H. Atom transfer radical polymerization. Chemical Reviews, 2001, 101(9): 2921–2990

[27] Pan K, Jiang L, Zhang J, . Reverse atom transfer radical polymerization of methyl methacrylate in different solvents. Journal of Applied Polymer Science, 2007, 106(4): 2543–2547

[28] Masci G, Giacomelli L, Crescenzi V. Atom transfer radical polymerization of N-isopropylacrylamide. Macromolecular Rapid Communications, 2004, 25(4): 559–564

[29] Destarac M, Matyjaszewski K, Silverman E, . Atom transfer radical polymerization initiated with vinylidene fluoride telomers. Macromolecules, 2000, 33(13): 4613–4615

[30] Zhang M, Russell T P. Graft copolymers from poly(vinylidene fluoride-co-chlorotrifluoroethylene) via atom transfer radical polymerization. Macromolecules, 2006, 39(10): 3531–3539

[31] Singh N, Husson S M, Zdyrko B, . Surface modification of microporous PVDF membranes by ATRP. Journal of Membrane Science, 2005, 262(1-2): 81–90

[32] Ciampolini M, Nardi N. Trigonal bipyramidal complexes of bivalent manganese, iron, and zinc with tris(2-dimethylaminoethyl)amine. Inorganic Chemistry, 1966, 5(7): 1150–1154

[33] Hesampour M, Huuhilo T, Makinen K, . Grafting of temperature sensitive PNIPAAm on hydrophilised polysulfone UF membranes. Journal of Membrane Science, 2008, 310(1-2): 85–92

[34] Yu H Y, Li W, Zhou J, . Thermo- and pH-responsive polypropylene microporous membrane prepared by the photoinduced RAFT-mediated graft copolymerization. Journal of Membrane Science, 2009, 343(1-2): 82–89

Acknowledgments

This work was financially supported by National Natural Science Foundation of China (Grant No. 20774064), Project of Science and Technical Development of China (Grant No. 2007AA03Z533), Key Grant Project of Chinese Ministry of Education (Grant No. 209005), and Science and Technical Development Foundation of Colleges and Universities, Tianjin, China (Grant No. 20071214).

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2014 Higher Education Press and Springer-Verlag Berlin Heidelberg