Preparation of Organic-inorganic Hybrid PES Membranes using Fe(II) Clathrochelate

Fe(II) clathrochelate을 이용한 유.무기 PES 복합막의 제조

  • Jung, Bo Ram (Institute of Industrial Technology, Dongeui University) ;
  • Son, Yeji (Department of Environmental Engineering, Dongeui University) ;
  • Lee, Yong Taek (College of Environment and Applied Chemistry, KyungHee University) ;
  • Kim, Nowon (Department of Environmental Engineering, Dongeui University)
  • 정보람 (동의대학교 산업기술개발연구소) ;
  • 손예지 (동의대학교 환경공학과) ;
  • 이용택 (경희대학교 환경.응용화학대학) ;
  • 김노원 (동의대학교 환경공학과)
  • Received : 2013.02.17
  • Accepted : 2013.02.25
  • Published : 2013.02.28

Abstract

Metal-templated condensation of cyclohexanedione dioxime and phenylboronic acid in the presence of Fe(II) sulfate heptahydrate proceeds cleanly in methanol to furnish the Fe(II) clathrochelate. An organic/inorganic hybrid membranes composed of Fe(II) clathrochelate and polyethersulfone was prepared by using phase inversion method. For membrane preparation, the Fe(II) clathrochelate was highly soluble (3~5 g/L) in DMF, NMP, and DMAc, which meets the requirements for the solubility of metal complexes in polar aprotic solvent used in membrane preparation. It was stable even in the presence of strong acids, such as trifluorosactic acid (pKa = 0.3). It was characterized by UV-vis spectroscopy, and their stability in solution phase studied in the presence of (i) strong acids or (ii) competing chelates. Organic/inorganic hybrid membranes were prepared with polyethersulfone, polyvinylpyrrolidone, p-toluenesulfonic acid, Fe(II) clathrochelate and DMF by using nonsolvent induced phase inversion method. The addition of Fe(II) clathrochelate leads increase of surface pore density, mean pore size and flux. We can obtain highly asymmetric membranes by addition of Fe(II) clathrochelate.

$Fe(SO_4)_2$, cyclohexanedione dioxime, phenylboronic acid을 이용하여 금속 템플레이트 중합을 실시한 후 메탄올로 세척하여 Fe(II) clathrochelate 화합물을 합성하였다. Fe(II) clathrochelate와 polyethersulfone을 이용한 유무기 복합 멤브레인을 제조하였다. 멤브레인 제조를 위하여 Fe(II) clathrochelate는 DMF, NMP, DMAC와 같은 멤브레인 제조에 이용되는 극성 아프로틱 용매에 잘 녹는 물질로 고안되었다. Fe(II) clathrochelate는 trifluorosactic acid와 같은 강산 존재하에서도 금속이 분리되지 않고 안정성이 유지되었다. UV-vis 분광법으로 용액 가용성을 확인하였으며 (i) 강산 및 (ii) 경쟁 킬레이트제를 이용하여 용액상의 안정성을 확인하였다. 유무기 복합막은 PES, PVP, TSA, Fe(II) clathrochelate를 DMF에 녹여 NIPS (비용매 유도 상전이) 방법으로 제조하였다. Fe(II) clathrochelate의 첨가는 표면의 기공 밀도의 향상, 평균기공 크기의 증가 및 유량 증가에 영향을 주었으며 상대적으로 비대칭 구조를 가지는 성능이 향상된 멤브레인을 얻을 수 있었다.

Keywords

References

  1. M. Mulder, "Basic principles of membrane technology", pp.71-89, Kluwer Academic Publishers, London (1996).
  2. M. Cheryan, "Ultrafiltration handbook", pp. 1-26, Technomic Publishing Company, Inc. (1998), Basel (1986).
  3. Z. Yi, L.-P. Zhu, Y.-F. Zhao, B.-K. Zhu, and Y.-Y. Xu, "An extending of candidate for the hydrophilic modification of polysulfone membranes from the compatibility consideration : The polyethersulfone-based amphiphilic copolymer as an example", J. Membr. Sci., 390, 48 (2012).
  4. S.-J. Shin, J.-P. Kim, H.-J. Kim., J.-H. Jeon, and B.-R. Min, "Preparation and characterization of polyethersulfone microfiltration membranes by a 2-methoxyethanol additive", Desalination, 186, 1 (2005). https://doi.org/10.1016/j.desal.2005.03.092
  5. Z.-L. Xu and F. Alsalhy Qusay, "Polyethersulfone hollow fiber ultrafiltration membranes prepared by PES/non-solvent/NMP solution", J. Membr. Sci., 233, 101 (2004). https://doi.org/10.1016/j.memsci.2004.01.005
  6. I. F. Wang, R. A. Morris, and R. F. Zepf, "Highly asymmetric, hydrophilic, microfiltration membranes having large pore diameters", U.S. Patent 6,939,468 (2005).
  7. R. Semiat, "Energy issues in desalination processes", Environmental Science & Technology, 42, 8193 (2008). https://doi.org/10.1021/es801330u
  8. K. P. Lee, T. C. Arnot, and D. Mattia, "A review of reverse osmosis membrane materials for desalination- Development to date and future potential", J. Membr. Sci., 370, 1 (2011). https://doi.org/10.1016/j.memsci.2010.12.036
  9. R. L. Mcginnis and M. Elimelech, "Global challenges in energy and water supply : the promise of engineered osmosis", Environmental Science & Technology, 42, 8625 (2008). https://doi.org/10.1021/es800812m
  10. D. J. Kim and S. Y. Nam, "Recent trend of organic/ inorganic composite membrane for polymer electrolyte membrane fuel cell", Membrane Journal, 22, 155 (2012).
  11. A. Razmjou, J. Mansouri, and V. Chen, "The effects of mechanical and chemical modification of $TiO_2$ nanoparticles on the surface chemistry, structure and fouling performance of PES ultrafiltration membranes", J. Membr. Sci., 378, 73 (2011). https://doi.org/10.1016/j.memsci.2010.10.019
  12. G. Y. Choi, H. H. Han, and Y. T. Lee, "Preparation of nanoporous ceramic membranes by sol-gel method and characterization of gas permeation", Membrane Journal, 18, 176 (2008).
  13. W. Zhao, J. Huang, B. Fang, S. Nie, N. Yi, B. Su, H. Li, and C. Zhao, "Modification of polyethersulfone membrane by blending semi-interpenetrating network polymeric nanoparticles", J. Membr. Sci., 369, 258 (2011). https://doi.org/10.1016/j.memsci.2010.11.065
  14. S. Qiu, L. Wu, X. Pan, L. Zhang, H. Chen, and C. Gao, "Preparation and properties of functionalized carbon nanotube/PSF blend ultrafiltration membranes", J. Membr. Sci., 342, 165 (2009). https://doi.org/10.1016/j.memsci.2009.06.041
  15. M. J. Kim, S. D. Lee, and K. H. Yeom, "Effect of inorganic salt additives on formation of phase inversion polyethersulfone ultrafiltration membrane", Membrane Journal, 12, 75 (2002).
  16. M. S. Lee and K. H. Yeom, "Preparation of PES-$TiO_2$ hybrid membranes and evaluation of membrane properties", Membrane Journal, 17, 219 (2007).
  17. G. Li, M. Kanezashi, and T. Tsuru, "Preparation of organic-inorganic hybrid silica membranes using organoalkoxysilanes : The effect of pendant groups", J. Membr. Sci., 379, 287 (2011). https://doi.org/10.1016/j.memsci.2011.05.071
  18. L. Y. Lafreniere and F. D. F. Talbot, "Effect of poly (vinylpyrrolidone) additive on the performance of poly (ether sulfone) ultrafiltration membranes", Ind. Eng., Chem., Res., 26, 2385 (1987). https://doi.org/10.1021/ie00071a035
  19. J. Y. Lai, F. C. Lin, C. C. Wang, and D. M. Wang, "Effect of nonsolvent additives on the porosity and morphology of asymmetric TPX membranes", J. Membr. Sci., 118, 49 (1996). https://doi.org/10.1016/0376-7388(96)00084-1
  20. J. Gribble and S. Wherland, "Electron transfer in a series of cobalt clathrochelates in nonaqueous solution", Inorg. Chem., 28, 2859 (1989). https://doi.org/10.1021/ic00313a032