Citation: Cong-Jun Gan, Xiao-Chen Xu, Xue-Wei Jiang, Feng Gan, Jie Dong, Xin Zhao, Qing-Hua Zhang. Fabrication of 6FDA-HFBAPP Polyimide Asymmetric Hollow Fiber Membranes and Their CO₂/CH₄ Separation Properties[J]. Chinese Journal of Polymer Science, ;2019, 37(8): 815-826. doi: 10.1007/s10118-019-2255-7 shu

Fabrication of 6FDA-HFBAPP Polyimide Asymmetric Hollow Fiber Membranes and Their CO₂/CH₄ Separation Properties

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China

Corresponding author: Xin Zhao, xzhao@dhu.edu.cn Qing-Hua Zhang, qhzhang@dhu.edu.cn
Received Date: 17 January 2019
Revised Date: 6 March 2019
Accepted Date: 1 January 2019
Available Online: 23 April 2019

In this work, poly(amide acid) solution, the precursor of polyimide, was synthesized by the reaction of 4,4′-(hexafluoroisopropylidene)diphthalicanhydride and 2,2-bis[4-(4-aminophenoxy)phenyl]-hexafluoropropanane in the solvent of N-methyl-2-pyrrolidone (NMP) and tetrahydrofuran (THF). Then, hollow fiber membranes for high flux gas separation were prepared by dry-jet wet spinning using the precursor solution of poly(amide acid) as the spinning dope and a subsequent imidization process. Silicone rubber was further coated outside the obtained hollow fiber membranes to repair the defects on the denser layer. The effects of internal, external coagulation bath ratios with air gap, and coating solution concentrations on the morphologies, structures, and separation performance of the membranes were studied. Results showed that the sponge-like support layer was formed when the content of NMP was increased from 50% to 90% in the internal coagulation bath. The outer surface of the membrane became denser when the water content in the external coagulation bath increased from 40% to 100%, and the separation coefficient of CO₂/CH₄ increased by 2 times. This value could reach up to 1.4 when the air gap was 6 cm. With tuning the mass fraction of silicone rubber as 5%, hollow fiber composite membranes with uniform coating layer and an improved separation coefficient of 5.4 could be obtained.
- Polyimide,
- Gas separation,
- Preparation conditions,
- Membrane structure,
- Permeability
1. [1]
  Appels, L.; Lauwers, J.; Degreve, J.; Helsen, L.; Lievens, B.; Willems, K.; Vanimpe, J.; Rewil, R. Anaerobic digestion in global bio-energy production: potential and research challenges. Renew. Sust. Energ. Rev. 2011, 15, 4295-4301. doi: 10.1016/j.rser.2011.07.121
2. [2]
  Favre, E.; Bounaceur, R.; Roizard, D. Biogas, membranes and carbon dioxide capture. J. Membr. Sci. 2009, 328, 11-14. doi: 10.1016/j.memsci.2008.12.017
3. [3]
  Favre, E. Membrane processes and postcombustion carbon dioxide capture: challenges and prospects. Chem. Eng. J. 2011, 171, 782-793 doi: 10.1016/j.cej.2011.01.010
4. [4]
  Wenten, I. G. Recent development in membrane science and its industrial applications. Songklanakarin J. Sci. Technol. 2002, 24, 1010-1024.
5. [5]
  Andriani, D.; Wresta, A.; Atmaja, T. D,; Saepudin, A. A review on optimization production and upgrading biogas through CO₂ removal using various techniques. Appl. Biochem. Biotech. 2014, 172, 1909-1928. doi: 10.1007/s12010-013-0652-x
6. [6]
  Du, N.; Park, H. Advances in high permeability polymeric membrane materials for CO₂ separations. Energ. Environ. Sci. 2012, 5, 7306-7322. doi: 10.1039/C1EE02668B
7. [7]
  Jung, C. H.; Lee, J. E.; Han, S. H.; Park H. B.; Lee, Y. M. Highly permeable and selective poly (benzoxazole-co-imide) membranes for gas separation. J. Membr. Sci. 2010, 350, 301-309. doi: 10.1016/j.memsci.2010.01.005
8. [8]
  Budd, P. M.; Mckeown, N. B. Highly permeable polymers for gas separation membranes. Polym. Chem. 2010, 1, 63-68. doi: 10.1039/b9py00319c
9. [9]
  Robeson, L. M. Correlation of separation factor versus permeability for polymeric membranes. J. Membr. Sci. 1991, 62, 165-185. doi: 10.1016/0376-7388(91)80060-J
10. [10]
  Robeson, L. M. The upper bound revisited. J. Membr. Sci. 2008, 320, 390-400. doi: 10.1016/j.memsci.2008.04.030
11. [11]
  Calle, M.; Garcia, C.; Lozano, A. E.; Delacampa, J. G.; Deabajo, J.; Alvarez, C. Local chain mobility dependence on molecular structure in polyimides with bulky side groups: Correlation with gas separation properties. J. Membr. Sci. 2013, 434, 121-129. doi: 10.1016/j.memsci.2013.01.054
12. [12]
  Carta, M.; Croad, M. Triptycene induced enhancement of membrane gas selectivity for microporous Tröger's base polymers. Adv. Mater. 2014, 26, 3526-3531. doi: 10.1002/adma.v26.21
13. [13]
  Ma, X.; Swaidan, R.; Belmabkhout, Y. Synthesis and gas transport properties of hydroxyl-functionalized polyimides with intrinsic microporosity. Macromolecules 2012, 45, 3841-3849. doi: 10.1021/ma300549m
14. [14]
  Kim, S.; Pechar, T. W.; Marand, E. Poly(imide siloxane) and carbon nanotube mixed matrix membranes for gas separation. Desalination 2006, 192, 330-339. doi: 10.1016/j.desal.2005.03.098
15. [15]
  Chen, X. Y.; Rodrigue, D.; Kaliaguine, S. Diamino-organosilicone APTMDS: A new cross-linking agent for polyimides membranes. Sep. Purif. Technol. 2012, 86, 221-233. doi: 10.1016/j.seppur.2011.11.008
16. [16]
  Qiu, W.; Xu, L.; Chen, C. C.; Paul, D. R.; Koros, W. J. Gas separation performance of 6FDA-based polyimides with different chemical structures. Polymer 2013, 54, 6226-6235. doi: 10.1016/j.polymer.2013.09.007
17. [17]
  Xu, L.; Zhang, C.; Rungta, M.; Koros, W. J. Formation of defect-free 6FDA-DAM asymmetric hollow fiber membranes for gas separations. J. Membr. Sci. 2014, 459, 223-232. doi: 10.1016/j.memsci.2014.02.023
18. [18]
  Qiu, X. Z.; Wang, Y. M.; Wang, L. N.; Zhou, M. Q.; Yuan, Q. Preparation and properties of soluble polyimide membranes containing polyether segment for gas separation. Chem. J. Chinese U. 2009, 30, 196-202.
19. [19]
  Wang, Z. G.; Liu, X.; Wang, D. Tröger's base-based copolymers with intrinsic microporosity for CO₂ separation and effect of Tröger's base on separation performance. Polym. Chem. 2014, 5, 2793-2800. doi: 10.1039/c3py01608k
20. [20]
  Smith, Z. P.; Freeman, B. D. Graphene Oxide: A new platform for high-performance gas- and liquid- separation membranes. Angew. Chem. Int. Edit. 2014, 53, 10286-10288. doi: 10.1002/anie.201404407
21. [21]
  Ahmad, F.; Lau, K. K.; Shariff, A. M.; Yeong Y. F. Temperature and pressure dependence of membrane permeance and its effect on process economics of hollow fiber gas separation system. J. Membr. Sci. 2013, 430, 44-55. doi: 10.1016/j.memsci.2012.11.070
22. [22]
  Labreche, Y.; Lively, R. P.; Rezaei, F.; Chen, G.; Jones, C. W.; Koros, W. J. Post-spinning infusion of poly(ethyleneimine) into polymer/silica hollow fiber sorbents for carbon dioxide capture. Chem. Eng. J. 2013, 221, 166-175. doi: 10.1016/j.cej.2013.01.086
23. [23]
  Ren, J.; Wang, R. The effects of chemical modifications on morphology and performance of 6FDA-ODA/NDA hollow fiber membranes for CO₂/CH₄ separation. J. Membr. Sci. 2003, 222, 133-147 doi: 10.1016/S0376-7388(03)00266-7
24. [24]
  Ma, C.; Zhang, C.; Labreche, Y.; Fu, S. L.; Liu, L.; Koros, W. J. Thin-skinned intrinsically defect-free asymmetric mono-esterified hollow fiber precursors for crosslinkable polyimide gas separation membranes. J. Membr. Sci. 2015, 493, 252-262 doi: 10.1016/j.memsci.2015.06.018
25. [25]
  Wienk, I.; Boom, R. Recent advances in the formation of phase inversion membranes made from amorphous or semi-crystalline polymers. J. Membr. Sci. 1996, 113, 361-371. doi: 10.1016/0376-7388(95)00256-1
26. [26]
  Reuvers, A.; Van, A. Formation of membranes by means of immersion precipitation: Part I. A model to describe mass transfer during immersion precipitation. J. Membr. Sci. 1987, 34, 45-65. doi: 10.1016/S0376-7388(00)80020-4
27. [27]
  Widjojo, N.; Chung, T. S. Thickness and air gap dependence of macrovoid evolution in phase-inversion asymmetric hollow fiber membranes. Ind. Eng. Chem. Res. 2006, 45, 7618-7626. doi: 10.1021/ie0606587
28. [28]
  Wang, D.; Li, K.; Teo, W. K. Highly permeable polyethersulfone hollow fiber gas separation membranes prepared using water as non-solvent additive. J. Membr. Sci. 2000, 176, 147-158. doi: 10.1016/S0376-7388(00)00419-1
29. [29]
  Hibshman, C.; Cornelius, C. J.; Marand, E. The gas separation effects of annealing polyimide-organosilicate hybrid membranes. J. Membrane Sci. 2003, 211, 25-40 doi: 10.1016/S0376-7388(02)00306-X
30. [30]
  Bondi, A. Van der Waals volumes and radii. J. Phys. Chem. 1964, 68, 441-451. doi: 10.1021/j100785a001
31. [31]
  Van, Krevelen, D. W.; Te Nijenhuis, K. Properties of polymers: Their correlation with chemical structure; their numerical estimation and prediction from additive group contributions. Elsevier, 2009
32. [32]
  Jiang, X. W.; Xiao, X.; Dong, J.; Xu, X. C.; Zhao, X.; Zhang, Q. H. Effects of non-TR-able codiamines and rearrangement conditions on the chain packing and gas separation performance of thermally rearranged poly(benzoxazole-co-imide) membranes. J. Membr. Sci. 2018, 564, 605-616. doi: 10.1016/j.memsci.2018.07.068
33. [33]
  Pinnau, I.; Koros, W. J. Structures and gas separation properties of asymmetric polysulfone membranes made by dry, wet, and dry/wet phase inversion. J. Appl. Polym. Sci. 1991, 43, 1491-1502. doi: 10.1002/app.1991.070430811
34. [34]
  Ji, D. W.; Xiao, C. F.; An, S. L.; Zhao, J.; Hao, J. Q.; Chen, K. K. Preparation of high-flux PSF/GO loose nanofiltration hollow fiber membranes with dense-loose structure for treating textile wastewater. Chem. Eng. J. 2019, 363, 33-42 doi: 10.1016/j.cej.2019.01.111
1. [1]
  Chengye Lou , Yu Hu , Yunjia Jiang , Lingyao Wang , Yuanbin Zhang . Borane cage hybrid supramolecular metal-organic frameworks (BSFs): Design, synthesis and gas separation performance. Chinese Journal of Structural Chemistry, 2026, 45(2): 100789-100789. doi: 10.1016/j.cjsc.2025.100789
2. [2]
  Zhenyu Ji , Yucheng Xiao , Yunzhe Zhou , Ting Zhao , Lingna Yang , Cheng Chen , Mingyan Wu , Maochun Hong . A stable Zr-MOF with trap-and-flow channels for efficient natural gas purification. Chinese Journal of Structural Chemistry, 2026, 45(4): 100862-100862. doi: 10.1016/j.cjsc.2025.100862
3. [3]
  Yongheng Ren , Yang Chen , Hongwei Chen , Lu Zhang , Jiangfeng Yang , Qi Shi , Lin-Bing Sun , Jinping Li , Libo Li . Electrostatically driven kinetic Inverse CO2/C2H2 separation in LTA-type zeolites. Chinese Journal of Structural Chemistry, 2024, 43(10): 100394-100394. doi: 10.1016/j.cjsc.2024.100394
4. [4]
  Jun-Xian Chen , Xian-Xian Xiao , Libo Li , Jinping Li , Rui-Biao Lin , Xiao-Ming Chen . Fine-tuning of Hofmann-type metal-organic frameworks for highly efficient separation of C4 olefins. Chinese Journal of Structural Chemistry, 2025, 44(12): 100744-100744. doi: 10.1016/j.cjsc.2025.100744
5. [5]
  Yue Qian , Zhoujia Liu , Haixin Song , Ruize Yin , Hanni Yang , Siyang Li , Weiwei Xiong , Saisai Yuan , Junhao Zhang , Huan Pang . Imide-based covalent organic framework with excellent cyclability as an anode material for lithium-ion battery. Chinese Chemical Letters, 2024, 35(6): 108785-. doi: 10.1016/j.cclet.2023.108785
6. [6]
  Yongqin Zhu , Zhenyu Ji , Yunzhe Zhou , Mingyan Wu . Immobilization of multiple hydrogen-bond acceptor sites in a stable cage-based framework for efficient C₂F₆ purification. Chinese Chemical Letters, 2026, 37(9): 111478-. doi: 10.1016/j.cclet.2025.111478
7. [7]
  Feng Zheng , Ruxun Yuan , Xiaogang Wang . “Research-Oriented” Comprehensive Experimental Design in Polymer Chemistry: the Case of Polyimide Aerogels. University Chemistry, 2024, 39(10): 210-218. doi: 10.12461/PKU.DXHX202404027
8. [8]
  Yuting Bai , Cenqi Yan , Zhen Li , Jiaqiang Qin , Pei Cheng . Preparation of High-Strength Polyimide Porous Films with Thermally Closed Pore Property by In Situ Pore Formation Method. Acta Physico-Chimica Sinica, 2024, 40(9): 2306010-0. doi: 10.3866/PKU.WHXB202306010
9. [9]
  Kaixin Lai , Ke Wang , Xinwei Tang , Tian Sun , Yan Li , Zhiwei Hu , Wei Li , Wei Hong , Wenkai Chen , Xinyi Jiang , Zicheng Wang , Tianxi Liu . Selective thermal radiation polyimide composite fabric for efficient infrared stealth and electromagnetic protection. Acta Physico-Chimica Sinica, 2026, 42(7): 100272-. doi: 10.1016/j.actphy.2026.100272
10. [10]
  Qi Li , Minqiao Liang , Huifen Zhuang , Zhengyang Chen , Yuxiang Jiang , Xiaofei Chen , Yifa Chen , Ya-Qian Lan . Underscoring the polyimide-linkage in covalent organic frameworks and related applications. Chinese Chemical Letters, 2026, 37(2): 111593-. doi: 10.1016/j.cclet.2025.111593
11. [11]
  Jie Ma , Jianxiang Wang , Jianhua Yuan , Xiao Liu , Yun Yang , Fei Yu . The regulating strategy of hierarchical structure and acidity in zeolites and application of gas adsorption: A review. Chinese Chemical Letters, 2024, 35(11): 109693-. doi: 10.1016/j.cclet.2024.109693
12. [12]
  Xiao-Yan Ran , Tian-Jian Xiong , Yu-Ping Yang , Zong-Hong Luo , Cheng Liu , Yu-Lan Zhu , Jun-Hui Zhang , Bang-Jin Wang , Sheng-Ming Xie , Li-Ming Yuan . Chiral porous liquid D-his-ZIF-8-[Bpy][NTf₂] for capillary gas chromatographic separation. Chinese Chemical Letters, 2026, 37(5): 111864-. doi: 10.1016/j.cclet.2025.111864
13. [13]
  Liangju Zhao , Shiyu Qin , Fei Wu , Limin Zhu , Qing Han , Lingling Xie , Xuejing Qiu , Hongliang Wei , Lanhua Yi , Xiaoyu Cao . Polycarbonyl conjugated porous polyimide as anode materials for high performance sodium-ion batteries. Chinese Chemical Letters, 2025, 36(8): 110246-. doi: 10.1016/j.cclet.2024.110246
14. [14]
  Jun-Hui Zhang , Rui-Xue Liang , Bin Huang , Li-Qin Yu , Juan Chen , Bang-Jin Wang , Sheng-Ming Xie , Li-Ming Yuan . Preparation of a homochiral metal-organic cage and its bonded silicas for efficient enantioseparation in high-performance liquid chromatography and gas chromatography. Chinese Chemical Letters, 2026, 37(1): 111146-. doi: 10.1016/j.cclet.2025.111146
15. [15]
  Yan Zou , Yin-Shuang Hu , Deng-Hui Tian , Hong Wu , Xiaoshu Lv , Guangming Jiang , Yu-Xi Huang . Tuning the membrane rejection behavior by surface wettability engineering for an effective water-in-oil emulsion separation. Chinese Chemical Letters, 2024, 35(6): 109090-. doi: 10.1016/j.cclet.2023.109090
16. [16]
  Changle Liu , Mingyuzhi Sun , Haoran Zhang , Xiqian Cao , Yuqing Li , Yingtang Zhou . All in one doubly pillared MXene membrane for excellent oil/water separation, pollutant removal, and anti-fouling performance. Chinese Journal of Structural Chemistry, 2024, 43(8): 100355-100355. doi: 10.1016/j.cjsc.2024.100355
17. [17]
  Xiaojie Sun , Xiaoyan Yang , Zitong Wang , Furui Qu , Xin Cong , Qingsong Fu , Chang Su , Xiguang Chen , Kai Shao , Zhiyu He , Chao Feng . The micro-nano electrospinning membrane with water repellenting separation effect for interface hemostasis and anti-adhesion. Chinese Chemical Letters, 2026, 37(8): 111841-. doi: 10.1016/j.cclet.2025.111841
18. [18]
  Linghai Han , Xue Gong , Yupeng Wang , Dan Wang , Chunyu Ru , Xian Wang , Donglai Guo , Fangbing Liu , Xia Sheng , Junjie Ge . Structure, design, and advanced characterization techniques of catalyst layers in proton exchange membrane fuel cells. Chinese Chemical Letters, 2026, 37(10): 111432-. doi: 10.1016/j.cclet.2025.111432
19. [19]
  Haotian Zhang , Shengfa Feng , Mufan Cao , Xiong Xiong Liu , Pengcheng Yuan , Yaping Wang , Min Gao , Long Pan , Zhengming Sun . Al₂O₃ coated polyimide porous films enable thin yet strong polymer-in-salt solid-state electrolytes for dendrite-free lithium metal batteries. Chinese Chemical Letters, 2025, 36(8): 111096-. doi: 10.1016/j.cclet.2025.111096
20. [20]
  Huihui LIU , Baichuan ZHAO , Tingting ZHANG , Chuanhui WANG , Zhi WANG , Congyun ZHANG . High-sensitivity surface-enhanced Raman scattering detection and self-cleaning performance of organic pollutants based on a filter membrane sandwich structure. Chinese Journal of Inorganic Chemistry, 2026, 42(6): 1299-1311. doi: 10.11862/CJIC.20260362

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(2491)
HTML views(70)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Fabrication of 6FDA-HFBAPP Polyimide Asymmetric Hollow Fiber Membranes and Their CO2/CH4 Separation Properties

Metrics

通讯作者: 陈斌, bchen63@163.com

Fabrication of 6FDA-HFBAPP Polyimide Asymmetric Hollow Fiber Membranes and Their CO₂/CH₄ Separation Properties