Membrane Journal (멤브레인)

The Membrane Society of Korea (한국막학회)
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Separation of Gas Based on PTMSP-silica-PEI Composites

PTMSP-silica-PEI 복합막에 의한 기체 분리에 관한 연구

  • Kang Tae-Bum (Department of Chemistry, Sang Myung University) ;
  • Hong Se-Lyung (Department of Chemistry, Sang Myung University)
  • Published : 2006.06.01
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Abstract

The PTMSP-silica-PEI composite membranes were synthesized from tetraethoxysilane (TEOS) and poly (1-trimethylsilyl-1-propyne) (PTMSP) by sol-gel process. The PTMSP-silica nanocomposite membranes were characterized by $^1H-NMR$, FT-IR, TGA, XPS, SEM, GPC and gas permeation measurements were accomplished with $H_2,\;O_2,\;N_2,\;CO_2,\;CH_4$. The gases permeability increased with increasing TEOS content. Both the permeability and selectivity of $H_2,\;CH_4$ increased to 15 wt% TEOS. While the permeability of $O_2,\;CO_2$ increased without decrease of selectivity.

PTMSP-silica-PEI 복합막이 PTMSP에 TEOS를 가하여 졸-겔 방법에 의해 제조되었다. 복합막의 특성은 $^1H-NMR$, FT-IR, TGA, XPS, SEM, GPC 등을 사용하여 조사하였고, 복합막의 기체투과 특성을 알아보기 위해 $H_2,\;O_2,\;N_2,\;CO_2,\;CH_4$를 사용하였다. PTMSP-silica-PEI 복합막의 기체 투과도는 TEOS의 함량이 증가함에 따라 증가하였다. $H_2$와 $CH_4$는 15 wt% TEOS에서 PTMSP-PEI 복합막보다 투과도와 선택도가 모두 증가하였다. 한편 $O_2$와 $CO_2$는 선택도의 감소없이 투과도가 증가하는 경향을 나타냈다.

Keywords

References

  1. S. P. Nunes, K. V. Peinemann, K. Ohlrogge, A. Alpers, M. Keller, and A. T. N. Pires, 'Membranes of poly(ether imide) and nanodispersed silica', J. Membrane Sci., 157, 219 (1999) https://doi.org/10.1016/S0376-7388(98)00379-2
  2. C. J. Cornelius and E. Marand, 'Hybrid silica-polyimide composite membranes : gas transport properties', J. Membrane Sci., 202, 97 (2002) https://doi.org/10.1016/S0376-7388(01)00734-7
  3. C. Joly, S. Goizet, J. C. Schrotter, J. Sanchez, and M. Escoubes, 'Sol-gel polyimide-silica composite membrane : gas transport properties', J. Membrane Sci., 130, 63 (1997) https://doi.org/10.1016/S0376-7388(97)00008-2
  4. H. B. Park, J. K. Kim, S. Y. Nam, and Y. M. Lee, 'Imide-siloxane block copolymer/silica hybrid membranes: preparation, characterization and gas separation properties', J. Membrane Sci., 220, 59 (2003) https://doi.org/10.1016/S0376-7388(03)00215-1
  5. M. Moaddeb and W. J. Koros, 'Gas transport properties of thin polymeric membranes in the presence of silicon dioxide particles', J. Membrane Sci., 125, 143 (1997) https://doi.org/10.1016/S0376-7388(96)00251-7
  6. Q. Hu, E. Marand, S. Dhingra, D. Fritsch, J. Wen, and G. Wilkes, '$Poly(amide-imide)/TiO_2$ nanocomposite gas separation membranes: fabrication and characterization', J. Membrane Sci., 135, 65 (1997) https://doi.org/10.1016/S0376-7388(97)00120-8
  7. S. P. Nunes, J. Schultz, and K. V. Peinemann, 'Silicone membranes with silica nanoparticles', J. Mater. Sci. Lett., 15, 1139 (1996) https://doi.org/10.1007/BF00539961
  8. T. C. Merkel, Z. He, I. Pinnau, B. D. Freeman, P. Meakin, and A. J. Hill, 'Effect of nanoparticles on gas sorption and transport in poly(l-trimethylsilyl-l-propyne)', Macromolecules, 36, 6844 (2003) https://doi.org/10.1021/ma0341566
  9. Z. He, I. Pinnau, and A. Morisato, 'Nanostructured poly(4-methyl-2-pentyne)/silica hybrid membranes for gas separation', Desalination, 146, 11 (2002) https://doi.org/10.1016/S0011-9164(02)00463-0
  10. I. Pinnau and Z. He, Filled superglassy membrane, US Patent 6,316,684 B1 (2001)
  11. T. C. Merkel, 'Organic-inorganic nanocomposite membranes for vapor separations', Ph.D. dissertation, North Carolina State University, USA (2001)
  12. T. C. Merkel, B. D. Freeman, R. J. Spontak, Z. He, I. Pinnau, P. Meakin, and A. J. Hill, 'Ultrapermeable reverse-selective nanocomposite membranes', Science, 296, 519 (2002) https://doi.org/10.1126/science.1069580
  13. M. Jia, K. V. Peinemann, and R. D. Behling, 'Molecular sieving effect of the zeolite-filled silicone rubber membrane in gas separation', J. Membrane Sci., 57, 289 (1991) https://doi.org/10.1016/S0376-7388(00)80684-5
  14. Kazukiyo Nagai, Toshio Masuda, Tsutomu Nakagawa, Benny D. Freeman, and Ingo Pinnau, 'Poly[1-(trimethylsilyl)-1-propyne] and related polymers: synthesis, properties and functions', Prog. Polym. Sci., 26, 721 (2001) https://doi.org/10.1016/S0079-6700(01)00008-9
  15. M. Langsam, M. Anand, and E. J. Karwacki, 'Substituted propyne polymers I. Chemical surface modification of poly[1-( trimethylsily1)propyne) for gas separation membranes', Gas Separation & Purification, 2, 162 (1988) https://doi.org/10.1016/0950-4214(88)80001-X
  16. I. Pinnau and L. G. Toy, 'Transport of organic vapors through poly(1-trimethylsilyl-1-propyne)', J. Membrane Sci., 116, 199 (1996) https://doi.org/10.1016/0376-7388(96)00041-5
  17. T. C. Merkel, V. Bondar, K. Nagai, and B. D. Freeman, 'Sorption and Transport of Hydrocarbon and Perfluorocarbon Gases in Poly(1-trimethylsilyl-1-propyne)', J. Polymer Sci.: Part B: Polymer Physics., 38, 273 (2000) https://doi.org/10.1002/(SICI)1099-0488(20000115)38:2<273::AID-POLB1>3.0.CO;2-X
  18. Toshio Masuda, Yuichiro Iguchi, Ben-Zhong Tang, and Toshinobu Higashimura, 'Diffusion and solution of gases in substituted polyacetylene membranes', Polymer, 29, 2041 (1988) https://doi.org/10.1016/0032-3861(88)90178-4
  19. A. C. Savoca, A. D. Surnamer, and Chao-fong Tien, 'Gas Transport in poly(silylpropynes): The Chemical Structure Point of View', Macromolecules, 26, 6211 (1993) https://doi.org/10.1021/ma00075a013
  20. Yu Nagase, Yuriko Takamura, and Kiyohide Matsui, 'Chemical Modification of Poly (substituted-Acetylene). V. Alkylsilylation of Poly(1-Trimethylsilyl-1-Propyne) and Improved Liquid Separating Property at Pervaporation', J. Applied Polymer Sci., 42, 185 (1991) https://doi.org/10.1002/app.1991.070420122
  21. Dominique Gomes, Suzana P. Nunes, and Klaus-Viktor Peinemann, 'Membranes for gas separation based on poly(1-trimethylsilyl-1-propyne)-silica nanocomposites', J. Membrane Sci., 246, 13 (2005) https://doi.org/10.1016/j.memsci.2004.05.015
  22. M. Langsam and L. M. Robeson, 'Substituted propyne polymers-Part II. Effects of aging on the gas permeability properties of poly[1-(trimethylsilyl) propyne] for gas separation membranes', Polymer Eng. Sci., 29(1), 44 (1989) https://doi.org/10.1002/pen.760290109
  23. Yu Nagase, Tomoko Ueda, Kiyohide Matsui, and Masaki Uchikura, 'Chemical Modification of poly(substituted-acetylene). I. Synthesis and Gas Permeability of Poly(1-trimethylsilyl-1-propyne)/ Poly (dimethylsiloxane) Graft Copolymer', J. Polymer Sci.: Part B: Polymer Physics, 29, 171 (1991) https://doi.org/10.1002/polb.1991.090290204
  24. K. Nagai, A. Higuchi, and T. Nakagawa, 'Bromination and Gas Permeability of poly(1-trimethylsilyl-1-propyne) Membrane', J. Applied Polymer Sci., 54, 1207 (1994) https://doi.org/10.1002/app.1994.070540903
  25. L. Starannikova, V. Khodzhaeva, and Yu. Yampolskii, 'Mechanism of aging of poly[1- (trimethylsilyl)-1-propyne] and its effect on gas permeability', J. Membrane Sci., 244, 183 (2004) https://doi.org/10.1016/j.memsci.2004.06.051
  26. Kazukiyo Nagai and Tsutomu Nakagawa, 'Effects of aging on the gas permeability and solubility in poly(1-trimethylsilyl-1-propyne) membranes synthesized with various catalysts', J. Membrane Sci., 105, 261 (1995) https://doi.org/10.1016/0376-7388(95)00065-K
  27. P. Winberg, K. Desitter, C. Dotremont, S. Mullens, I. F. J. Vankelecom, and F. H. J. Maurer, 'Free volume and interstitial mesopores in silica filled poly(1-trimethylsilyl-1-propyne) nanocomposites', Macromolecules, 38, 3776 (2005) https://doi.org/10.1021/ma047369j
  28. K.Takada, H. Matsuya, T. Masuda, and T. Higashimura, 'Gas-permeability of polyacetylenes carrying substituents', J. Applied Polymer Sci., 30, 1605 (1985) https://doi.org/10.1002/app.1985.070300426
  29. T. B. Kang, H. K. Lee, and S. H. Cho, 'Separation of $H_2-N_2$ Gas Mixture by PTMSP-PEI and PDMS-PEI Composite Membranes', Membrane Journal, 13(4), 291 (2003)
  30. J. M. Watson and P. A. Payne, 'A study of organic compound pervaporation through silicone rubber', J. Membrane Sci., 49, 171 (1990) https://doi.org/10.1016/S0376-7388(00)80786-3
  31. J. M. Watson and M. G. Baron, 'Precise static and dynamic permeation measurements using a continuous-flow vacuum cell', J. Membrane Sci., 106, 259 (1995) https://doi.org/10.1016/0376-7388(95)00090-Y
  32. R. M. Felder and G. S. Huvard, 'Permeation, diffusion and sorption of gases and vapors', in: R. A. Fava (Ed.), Methods of Experimental Physics (Polymers) 16, Academic Press, New York (1981)
  33. T. Masuda, E. Isobe, and T. Higashimura, 'Polymerization of 1-(trimethylsilyl)-1-propyne by halides of niobium(V) and tantalum(V) and polymer properties', Macromolecules, 18, 841 (1985) https://doi.org/10.1021/ma00147a003
  34. Shun-He Zhong, Chuan-Feng Li, and Xiu-Fen Xiao, 'Preparation and characterization of polyimide-silica hybrid membranes on kieselguhr-mullite supports', J. Membrane Sci., 199, 53 (2002) https://doi.org/10.1016/S0376-7388(01)00676-7
  35. John F. Moulder, William F. Stickle, Peter E. Sobol, and Kenneth D. Bomben, Handbook of X-Ray Photoelectron Spectroscopy, (1992)
  36. M. Adachi, Y. Suzuki, N. Kashiwagi, T. Isobe, and M. Senna, 'Preparation and properties of polymer microspheres dispersed in a silica gel film', Colloids Surfaces A: Physiochem. Eng. Aspects, 153, 617 (1998)
  37. T. C. Merkel, V. Bondar, K. Nagai, and B. D. Freeman, 'Sorption and Transport of Hydrocarbon and Perfluorocarbon Gases in Poly(1-trimethylsilyl-1-propyne)', J. Polymer Science: Part B: Polymer Physics, 38, 273 (2000) https://doi.org/10.1002/(SICI)1099-0488(20000115)38:2<273::AID-POLB1>3.0.CO;2-X
  38. Kristien De Sitter, Petra Winberg, Jan D'Haen, Chris Dotremont, Roger Leysen, Johan A. Martens, Steven Mullens, Frans H. J. Maurer, and Ivo F. J. Vankelecom, 'Silica filled poly(1-trimethylsilyl-1-propyne) nanocomposite membrnae: Relation between the transport of gases and structural characteristics', J. Membrane Sci., 278, 83 (2006) https://doi.org/10.1016/j.memsci.2005.10.046