聚酰亞胺（PI）膜由於其優異的性能（例如耐熱性，良好的機械強度和良好的耐化學性）而被廣泛考慮並長期用於各種應用中，特別是在分離領域。但是，PI基薄膜具有溶解度限制，只能溶解在強極性溶劑（例如DMSO或DMF）中，這在一定程度上阻礙了製造過程。因此，迫切需要不使用有機溶劑來製備水溶性PI基膜。在這項研究中，製備了一些完全基於脂肪族基團的親水性PI前體，並通過GPC，NMR和ATR-FTIR技術對其進行了表徵，以確認其結構和性能。通過甲矽烷基化聚合成功地形成了四種高分子量（20000 g.mol-1以上）的聚酰胺酸。聚砜（PSf）膜已被改性。通過滴鑄法塗佈水溶性PAA時，親水性高，接觸角值從90o減小到54o。改性膜在氣體分離過程中具有微小的傾斜角，選擇CO2氣體（α〜0.8）。

Polyimide (PI) membranes have been widely considered and used in various applications for a long time, especially in the field of separation, due to their excellent properties (such as heat resistance, good mechanical strength, and good chemical resistance). However, PI-based films have solubility limitations, which can only be dissolved in strong polar solvents such as DMSO or DMF, which hinders the manufacturing process to some extent. Therefore, there is an urgent need to prepare water-soluble PI-based films without using organic solvents. In this study, some hydrophilic PI precursors based entirely on aliphatic groups were prepared and characterized by GPC, NMR, and ATR-FTIR techniques to confirm their structure and properties. Four types of poly (amic acid) with high molecular weight (above 20000 g.mol-1) were successfully formed through silylation polymerization. The polysulfone (PSf) membrane has been modified. When coated with water-soluble PAA by the drop-casting method. It is highly hydrophilic, and the contact angle value is reduced from 90o to 54o. The modified membrane has a slight inclination angle in the gas separation process to select CO2 gas (α~0.8).

REFERENCE

[1] Ramlogan, R. (1997). Environment and human health: A threat to all. Environmental Management and Health, 8(2), 51-66.
[2] Quadrelli, R., & Peterson, S. (2007). The energy–climate challenge: Recent trends in CO2 emissions from fuel combustion. Energy policy, 35(11), 5938-5952.
[3] Wang P, Wang M, Liu F, Ding S, Wang X, Du G, Liu J, Apel P, Kluth P, Trautmann C, Wang Y. Ultrafast ion sieving using nanoporous polymeric membranes. Nature communications. 2018 Feb 8;9(1):569.
[4] Warsinger DM, Chakraborty S, Tow EW, Plumlee MH, Bellona C, Loutatidou S, Karimi L, Mikelonis AM, Achilli A, Ghassemi A, Padhye LP. A review of polymeric membranes and processes for potable water reuse. Progress in Polymer Science. 2018 Jan 31.
[5] Koros WJ, Zhang C. Materials for next-generation molecularly selective synthetic membranes. Nature materials. 2017 Mar;16(3):289.
[6] Yang, S. Y. (Ed.). (2018). Advanced Polyimide Materials: Synthesis, Characterization, and Applications. Elsevier.
[7] Sanders DF, Smith ZP, Guo R, Robeson LM, McGrath JE, Paul DR, Freeman BD. Energy-efficient polymeric gas separation membranes for a sustainable future: A review. Polymer. 2013 Aug 16;54(18):4729-61.
[7] Rafiq, Sikander, Zakaria Man, Saikat Maitra, Abdulhalim Maulud, Farooq Ahmad, and Nawshad Muhammad. "Preparation of asymmetric polysulfone/polyimide blended membranes for CO 2 separation." Korean Journal of Chemical Engineering 28, no. 10 (2011): 2050-2056.
[8] Hu, J., Cai, H., Ren, H., Wei, Y., Xu, Z., Liu, H., & Hu, Y. (2010). Mixed-matrix membrane hollow fibers of Cu3 (BTC) 2 MOF and polyimide for gas separation and adsorption. Industrial & Engineering Chemistry Research, 49(24), 12605-12612.
[9] Dorosti, F., Omidkhah, M. R., Pedram, M. Z., & Moghadam, F. (2011). Fabrication and characterization of polysulfone/polyimide–zeolite mixed matrix membrane for gas separation. Chemical Engineering Journal, 171(3), 1469-1476.
[10] Hamid, M. A. A., Chung, Y. T., Rohani, R., & Junaidi, M. U. M. (2019). Miscible-blend polysulfone/polyimide membrane for hydrogen purification from palm oil mill effluent fermentation. Separation and Purification Technology, 209, 598-607.
[12] Padavan, D. T., & Wan, W. K. (2010). Synthesis and characterization of a novel versatile polyamicacid derived from ethylenediaminetetraacetic dianhydride. Materials Chemistry and Physics, 124(1), 427-433.
[13] Hsiao, P. F., Anbazhagan, R., Hsiao-Ying, C., Vadivelmurugan, A., & Tsai, H. C. (2017). Thermoresponsive polyamic acid-conjugated gold nanocarrier for enhanced light-triggered 5-fluorouracil release. RSC Advances, 7(14), 8357-8365.
[14] Werber JR, Osuji CO, Elimelech M. Materials for next-generation desalination and water purification membranes. Nature Reviews Materials. 2016 May;1(5):16018.
[15] Kamaruddin, H.D.; and Koros, W.J. (1997). Some observations about the application of Fick’s first law for membrane separation of multi-component mixture. Journal of Membrane Science, 135, 147-159.
[16] Koros, W. J., Paul, D. R., & Rocha, A. A. (1976). Carbon dioxide sorption and transport in polycarbonate. Journal of Polymer Science: Polymer Physics Edition, 14(4), 687-702.
[17] Chong, K. C.; Lai, S. O.; Thiam, H. S.; Teoh, H. C.; Heng, S. L. (2016). "Recent progress of oxygen/nitrogen separation using membrane technology". Journal of Engineering Science and Technology. 11 (7): 1016–1030.
[18] Rao, H.-X.; Liu, F.-N; and Zhang, Z.-Y. (2007). Oxygen-enriching properties of silicone rubber crosslinked membrane containing cobalt. Journal of Membrane Science, 296, 15-20.
[19] Hosseini, S.S.; Omidkhah, M.R.; Moghaddam, A.Z.; Pirouzfar, V.; Krantz, W.B.; and Tan, N.R. (2014). Enhancing the properties and gas separation performance of PBI-polyimides blend carbon molecular sieve membranes via optimization of the pyrolysis process. Separation and Purification Technology, 122, 278-289
[20] Abadie, M. (2012). High Performance Polymers - Polyimides Based - From Chemistry to Applications.
[21] Chen, X., Yang, J., & Zhao, J. (2018). The effect of solvent to the kinetics of imidization of poly (amic acid). Polymer, 143, 46-51. doi:10.1016/j.polymer.2018.04.005
[22] Deligöz, H., Özgümüş, S., Yalçınyuva, T., Yıldırım, S., Deǧer, D., & Ulutaş, K. (2005). A novel cross-linked polyimide film: synthesis and dielectric properties. Polymer, 46(11), 3720-3729. doi:10.1016/j.polymer.2005.02.097
[23] García, M. G., Marchese, J., & Ochoa, N. A. (2010). Aliphatic–aromatic polyimide blends for H2 separation. International Journal of Hydrogen Energy, 35(17), 8983-8992. doi:10.1016/j.ijhydene.2010.06.038
[24] Georgiev, A., Dimov, D., Spassova, E., Assa, J., Dineff, P., & Danev, G. (2012). Chemical and Physical Properties of Polyimides: Biomedical and Engineering Applications. In High Performance Polymers - Polyimides Based - From Chemistry to Applications.
[25] Goh, P. S., Naim, R., Rahbari-Sisakht, M., & Ismail, A. F. (2019). Modification of membrane hydrophobicity in membrane contactors for environmental remediation. Separation and Purification Technology, 227. doi:10.1016/j.seppur.2019.115721
[26] Huang, S.-H., Hu, C.-C., Lee, K.-R., Liaw, D.-J., & Lai, J.-Y. (2006). Gas separation properties of aromatic poly(amide-imide) membranes. European Polymer Journal, 42(1), 140-148. doi:10.1016/j.eurpolymj.2005.06.032
[27] Kumar, A., Tateyama, S., Yasaki, K., Ali, M. A., Takaya, N., Singh, R., & Kaneko, T. (2016). (1)H NMR and FT-IR dataset based structural investigation of poly(amic acid)s and polyimides from 4,4'-diaminostilbene. Data Brief, 7, 123-128. doi:10.1016/j.dib.2016.02.006
[28] Lau, W. J., Gray, S., Matsuura, T., Emadzadeh, D., Chen, J. P., & Ismail, A. F. (2015). A review on polyamide thin film nanocomposite (TFN) membranes: History, applications, challenges and approaches. Water Res, 80, 306-324. doi:10.1016/j.watres.2015.04.037
[29] Lau, W. J., Ismail, A. F., Misdan, N., & Kassim, M. A. (2012). A recent progress in thin film composite membrane: A review. Desalination, 287, 190-199. doi:10.1016/j.desal.2011.04.004
[30] Li, B., Liu, T., & Zhong, W.-H. (2011). High modulus aliphatic polyimide from 1, 3-diaminopropane and ethylenediaminetetraacetic dianhydride: Water soluble to self-patterning. Polymer, 52(22), 5186-5192. doi:10.1016/j.polymer.2011.09.005
[31] Liu, Q., Paul, D. R., & Freeman, B. D. (2016). Gas permeation and mechanical properties of thermally rearranged (TR) copolyimides. Polymer, 82, 378-391. doi:10.1016/j.polymer.2015.11.051
[32] Mathews, A. S., Kim, I., & Ha, C.-S. (2006). Fully aliphatic polyimides from adamantane-based diamines for enhanced thermal stability, solubility, transparency, and low dielectric constant. Journal of Applied Polymer Science, 102(4), 3316-3326. doi:10.1002/app.24800
[33] Moura Bernardes, A. (2014). General Aspects of Membrane Separation Processes. In Electrodialysis and Water Reuse (pp. 3-9).
[34] Muñoz, D. M., Calle, M., de la Campa, J. G., de Abajo, J., & Lozano, A. E. (2009). An Improved Method for Preparing Very High Molecular Weight Polyimides. Macromolecules, 42(15), 5892-5894. doi:10.1021/ma9005268
[35] Ni, H.-j., Liu, J.-g., Wang, Z.-h., & Yang, S.-y. (2015). A review on colorless and optically transparent polyimide films: Chemistry, process and engineering applications. Journal of Industrial and Engineering Chemistry, 28, 16-27. doi:10.1016/j.jiec.2015.03.013
[36] Okello, V. A., Du, N., Deng, B., & Sadik, O. A. (2011). Environmental applications of poly(amic acid)-based nanomaterials. J Environ Monit, 13(5), 1236-1245. doi:10.1039/c1em10061k
[37] Padavan, D. T., & Wan, W. K. (2010). Synthesis and characterization of a novel versatile poly(amic acid) derived from ethylenediaminetetraacetic dianhydride. Materials Chemistry and Physics, 124(1), 427-433. doi:10.1016/j.matchemphys.2010.06.061
[38] Park, C.-Y., Kim, E.-H., Kim, J. H., Lee, Y. M., & Kim, J.-H. (2018). Novel semi-alicyclic polyimide membranes: Synthesis, characterization, and gas separation properties. Polymer, 151, 325-333. doi:10.1016/j.polymer.2018.07.052
[39] Vanherck, K., Koeckelberghs, G., & Vankelecom, I. F. J. (2013). Crosslinking polyimides for membrane applications: A review. Progress in Polymer Science, 38(6), 874-896. doi:10.1016/j.progpolymsci.2012.11.001
[40] Wu, S. Y., Chang, L. T., Peng, S., & Tsai, H. C. (2015). Calcium-activated gene transfection from DNA/poly(amic acid-co-imide) complexes. Int J Nanomedicine, 10, 1637-1647. doi:10.2147/IJN.S76502
[41] Yu, H.-C., Kumar, S. V., Choi, J., Kudo, K., Jang, Y.-H., & Chung, C.-M. (2012). Effect of unsymmetrical dianhydride structure on properties of fully aliphatic polyimides. High Performance Polymers, 24(5), 418-424. doi:10.1177/0954008312441641
[42] Zhuang, Y., Seong, J. G., & Lee, Y. M. (2019). Polyimides containing aliphatic/alicyclic segments in the main chains. Progress in Polymer Science, 92, 35-88. doi:10.1016/j.progpolymsci.2019.01.004