DOI QR코드

DOI QR Code

Study on Morphology Control of Polymeric Membrane with Clathrochelate Metal Complex

Clathrochelate계 금속 착물을 이용한 고분자 멤브레인 구조 제어

  • Kim, Nowon (Department of Environmental Engineering, Dong-Eui University) ;
  • Jung, Boram (Institute of Industrial Technology, Dongeui University)
  • 김노원 (동의대학교 환경공학과) ;
  • 정보람 (동의대학교 산업기술개발연구소)
  • Received : 2014.12.13
  • Accepted : 2014.12.17
  • Published : 2014.12.31

Abstract

This study is preparation of microporous membranes by using macrocyclic metal ion complexes and extended cage complexes. It is a more favorable way to existing methods because polymer and metal ion-ligand complex system provides a fine control over the phase transition behavior. Chemical functionalization of the polar surface can be obtained. Metal-templated condensation of cyclohexanedione dioxime, hydroxyphenylboronic acid in the presence of metal salts proceeds cleanly in methanol to furnish the metal clathrochelate complexes. Organic/inorganic hybrid membranes were prepared with polyethersulfone (PES), polyvinylpyrrolidone (PVP), ethyleneglycol butyl ether (BE), metal clathrochelate s and DMF by using nonsolvent induced phase inversion method. The structure of membranes was characterized with scanning electron microscopy (SEM) and microflow permporometer. The addition of Fe(II) clathrochelate complex with p-hydroxyphenyl group leads to changes of membrane morphology such as narrow mean pore size distribution, increase of surface pore density and decrease of the largest pore size.

본 연구는 거대고리 금속 이온 착화합물과 유도체를 이용하여 미세 다공성 구조를 가지는 분리막의 제조에 관한 것이다. 고분자와 금속이온 리간드 착물 시스템을 이용함으로써 기존의 방법들에 비해 상 전이 과정을 보다 정교하게 제어할 수 있었다. 금속염, cyclohexanedione dioxime, hydroxyphenylboronic acid와의 축합 반응을 통하여 금속 clathrochelate 착물을 얻을 수 있었다. PES, PVP, BE와 금속 clathrochelate 착물을 DMF에 녹인 후 비용매 유도 상 전이법을 통하여 유무기 혼성고분자막을 제조하였다. 제조된 분리막의 구조는 FE-SEM과 microflow permporometer로 조사하였다. p-Hydroxyphenyl group을 가지는 Fe(II) clathrochelate 착물의 첨가는 분리막의 구조에 있어 기공 크기 분산도를 좁혀주고, 표면의 기공 밀도를 높여 주었으며 최대 기공 크기를 감소시킴을 볼 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. R. M. Boom, I. M. Wienk, Th. Van den Boomgaard, and C. A. Smolders, "Microstructures in phase inversion membranes. Part 2. The role of a polymeric additive", J. Membr. Sci., 73, 277 (1992). https://doi.org/10.1016/0376-7388(92)80135-7
  4. I. M. Wienk, R. M. Boom, M. A. M. Beerlage, A.M. W. Bulte, and C. A. Smolders, "Recent advances in the formation of phase inversion membranes made from amorphous or semi-crystalline polymers", J. Membr. Sci., 113, 361 (1996). https://doi.org/10.1016/0376-7388(95)00256-1
  5. D. B. Mosqueda-Jimenez, R. M. Narbaitz, T. Matsuura, G. Chowdhury, G. Pleizier, and J. P. Santerre, "Influence of processing conditions on the properties of ultrafiltration membranes", J. Membr. Sci., 231, 209 (2004). https://doi.org/10.1016/j.memsci.2003.11.026
  6. 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
  7. 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
  8. C. Stropnik and V. Kaiser, "Polymeric membranes preparation by wet phase separation: mechanisms and elementary processes", Desalination, 145, 1 (2002). https://doi.org/10.1016/S0011-9164(02)00322-3
  9. B. K. Park, S. H. Kong, and S. Y. Nam, "Phase behavior and morphological studies of polysulfone membranes; The effect of alcohols used as a nonsolvent coagulant", Membrane Journal, 15, 272 (2005).
  10. B. Chakrabarty, A. K. Ghoshal, and M. K. Purkait, "Effect of molecular weight of PEG on membrane morphology and transport properties", J. Membr. Sci., 309, 209 (2008). https://doi.org/10.1016/j.memsci.2007.10.027
  11. Y. Ma, F. Shi, M. Wu, J. Zhang, and C. Gao, "Effect of PEG additive on the morphology and performance of polysulfone ultrafiltration membranes", Desalination, 272, 51 (2011). https://doi.org/10.1016/j.desal.2010.12.054
  12. D. Ranaa, T. Matsuuraa, and R. M. Narbaitzb, "Novel hydrophilic surface modifying macromolecules for polymeric membranes: Polyurethane ends capped by hydroxy group", J. Membr. Sci., 282, 205 (2006). https://doi.org/10.1016/j.memsci.2006.05.024
  13. M.-J. Han, Effect of propionic acid in the casting solution on the characteristics of phase inversion polysulfone membranes, Desalination, 121, 31 (1999). https://doi.org/10.1016/S0011-9164(99)00005-3
  14. N. Kim, C.-S. Kim, and Y.-T. Lee, "Preparation and characterization of polyethersulfone membranes with p-toluenesulfonic acid and polyvinylpyrrolidone additives", Desalination, 233, 218 (2008). https://doi.org/10.1016/j.desal.2007.09.046
  15. M.-J. Han, Effect of propionic acid in the casting solution on the characteristics of phase inversion polysulfone membranes, Desalination, 121, 31 (1999). https://doi.org/10.1016/S0011-9164(99)00005-3
  16. M. Han, "Effect of Nonsolvent Additive in Casting Solutions on Polysulfone Membrane Preparation", Membrane Journal, 6, 157 (1996).
  17. S. J. Oh, N. Kim, and Y. T. Lee, "Preparation and characterization of PVDF/TiO2 organic-inorganic compositemembranes for fouling resistance improvement", J. Membr. Sci., 345, 13 (2009). https://doi.org/10.1016/j.memsci.2009.08.003
  18. J. Gribble and S. Wherland, "Electron transfer in a series of cobalt clathrochelate s in nonaqueous solution", Inorg. Chem., 28, 2859 (1989). https://doi.org/10.1021/ic00313a032
  19. B. Jung, Y. Son, Y. T. Lee, and N. Kim, "Preparation of Organic-inorganic Hybrid PES Membranes using Fe(II) Clathrochelate", Membrane Journal, 23, 80 (2013).
  20. N. Kim, C.-S. Kim, and Y.-T. Lee, "Preparation and characterization of polyethersulfone membranes with p-toluenesulfonic acid and polyvinylpyrrolidone additives", Desalination, 233, 218 (2008). https://doi.org/10.1016/j.desal.2007.09.046