膜科学与技术

高通量自聚微孔聚酰亚胺富氧膜的制备

作者：徐浩，刘凌宇，刘清潭，储家琛，李建新，马小华

单位：天津工业大学材料科学与工程学院，省部共建分离膜与膜过程国家重点实验室，天津300387

关键词：聚酰亚胺；非对称膜；复合膜；氧氮分离

出版年,卷(期):页码： 2024,44(3):21-29

摘要：

开发高通量富氧膜对空气富氧和原位制氮具有重要意义。本工作以2，4，6-三甲基间苯二胺、4，4' -（六氟异亚丙基）二邻苯二甲酸酐和均苯四甲酸酐为单体，采用高温一步法制备了一种三元聚酰亚胺6FPDM。使用核磁、FT-IR、TGA探究了该聚酰亚胺的化学结构和热性能。使用非溶剂诱导相分离法，通过控制铸膜液成分、添加剂、凝固浴温度、相转化时间、刮刀厚度和PMDS涂层等对膜材料的相结构、分离性能进行调控。结果表明，通过控制铸膜液成分和相转化条件（质量分数为15 % 无水乙醇、质量分数为1% LiNO3、45 ℃的凝固浴和100 μm的刮刀厚度）所制的相转化膜，在经过涂覆后，其氧气的通量达到了96.9 GPU，氧/氮选择性达到了4.3，在膜法富氧方面显示出了非常优异的应用前景。

A ternary copolyimide 6FPDM was prepared using 2, 4, 6-trimethyl M-phenylenediamine (DAM), 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and pyromellitic anhydride (PMDA) as monomers by one-step high temperature polymerization method. By using non solvent induced phase separation method (NIPs), the completion time of phase separation is controlled by controlling the casting solution composition, coagulation bath temperature, additives and membrane thickness. Then, a PMDS layer is coated on the surface of the membrane to prepare the composite membrane. The oxygen/nitrogen separation performance of the polyimide pristine membrane, asymmetric membrane and composite membrane were tested. By regulating the dope solution and phase inversion conditions (15 wt.% absolute ethanol, 1 wt.% LiNO3, coagulation bath at 45 oC, and casting knife thickness of 100 μm), the resulted membrane displayed best gas permeability after coating. The oxygen flux reached 96.9 GPU, and the O2/N2 selectivity of 4.3, which has shown great potential in membrane-based oxygen enrichment field.

徐浩（1999-），男，内蒙古兴安盟人，研究生，研究方向为聚合物气体分离膜

参考文献：

[1] Micari M, Agrawal K V. Oxygen enrichment of air. Performance guidelines for membranes based on techno-economic assessment[J]. J Membr Sci, 2022, 641(1):119883.
[2] Seong J G, Lewis J C,Matteson J A. Polybenzimidazole-derived carbon molecular sieve hollow fiber membranes with tailored oxygen selective transport[J].Carbon, 2022, 192(13):71-83.
[3] Li G Q, Kujawskiet, Robert Valek, et al. A review-The development of hollow fiber membranes for gas separation processes[J]. Inter J Greenh Gas Control, 2021, 104: 103195.
[4] Sharpe I D, Ismail A F, S.J. Shilton. A study of extrusion shear and forced convection residence time in the spinning of polysulfone hollow fiber membranes for gas separation[J]. Sep Purif Technol, 1999, 17(2):101-109.
[5] Ghosal K, Chern R T, BD Freeman, et al. Effect of Basic Substituents on Gas Sorption and Permeation in Polysulfone[J]. Macromolecules, 1996, 29(12): 4360-4369.
[6] Takeuchi K, Cruz-Silva R, M Fujishige, et al. Preparation of polysulfone support for higher-performance reverse osmosis membranes. J Environ Chem Eng 2022, 10(3): 107860.
[7] Lu X, Elimelech M. Fabrication of desalination membranes by interfacial polymerization: history, current efforts, and future directions[J]. Chem Soc Rev, 2021, 50, 6290–6307
[8] Mulder M. Basic Principles of Membrane Technology [M]. Kluwer Academic Publishers 1996.
[9] 雷瑞, 高性能聚酰亚胺研究进展[J]. 合成工业纤维, 2014, 37 (3): 53-55.
[10] Dl W, Wk T, Li K. Preparation and characterization of polyetherimide asymmetric hollow fiber membranes for gas separation[J]. J Membr Sci, 1998, 138(2):193-201.
[11] Clausi D T, William J Koros. Formation of defect-free polyimide hollow fiber membranes for gas separations[J]. J Membr Sci, 2000, 167(1):79-89.
[12] Holden W H, Benedetti F M, Ahn J M., et al. Hydrocarbon ladder polymers with ultrahigh permselectivity for membrane gas separations.Science, 2022, 375(6587):1390 -1392.
[13] Budd P M, Ghanem B S, Makhseed S, et al. Polymers of intrinsic microporosity (PIMs): robust solution processable, organic nanoporous materials [J]. Chem Commun, 2004, 2 (2): 230-231
[14] Ye C, Luo C, W Ji et al. Significantly enhanced gas separation properties of microporous membranes by precisely tailoring their ultra-microporosity through bromination/debromination[J]. Chem Eng Technol, 2022, 451(1):138513.
[15] Ogieglo W, Puspasari T, Alabdulaaly A, et al. Gas separation performance and physical aging of tubular thin-film composite carbon molecular sieve membranes based on a polyimide of intrinsic microporosity precursor[J]. J Membr Sci, 2022, 652 (15):120497.
[16] Ye C, Luo C, W Ji, et al. Significantly enhanced gas separation properties of microporous membranes by precisely tailoring their ultra-microporosity through bromination/debromination[J]. J Membr Sci, 2022, 669(5):121310.
[17] Li G, Si Z, Yang S, et al.Fast layer-by-layer assembly of PDMS for boosting the gas separation of P84 membranes[J]. Chem Eng Sci, 2022, 253(5):117588.
[18] 于道明, 李凯华, 董昊, 等. 高性能聚酰亚胺氧气/氮气分离膜的设计与制备[J]. 膜科学与技术, 2021, 41(6):67-74.
[19] Chu J, Liu Q, Ji W, et al. Novel microporous sulfonated polyimide membranes with high energy efficiency under low ion exchange capacity for all vanadium flow battery[J].Electrochim Acta, 2023, 446(1):142080.
[20] Xu L R, Zhang C, Rungta M, et al. Formation of defect-free 6FDA-DAM asymmetric hollow fiber membranes for gas separations[J]. J Membr Sci, 2014, 459(1): 223-232.
[21] Li S G, Boomgard T V D, Smolders CA, et al. Physical Gelation of Amorphous Polymers in a Mixture of Solvent and Nonsolvent[J]. Macromolecules, 1996, 29(6): 2053-2059.
[22] Gumba N N, Hu M, Mamba Bhekie B, et al. Macrovoid-free PES/SPSf/O-MWCNT ultrafiltration membranes with improved mechanical strength, antifouling and antibacterial properties[J]. J Membr Sci, 2018, 56(6): 288-300.
[23] Zhao S, Wang Z, Wang J, et al. The effect of pH of coagulationbath on tailoring the morphology and separation performance of polysulfone/polyaniline ultrafiltration membrane[J]. J Membr Sci, 2014, 469(1):316–-325.
[24] Feng X, Shao P, Huang R, et al. A Study of Silicone Rubber/Polysulfone Composite Membranes: Correlating H2/N2 and O2/N2 Permselectivities[J]. Sep Purif Technol, 2002, 27(3):211-223.
[25] Kim K J, Park S H, So Wong W, et al. CO2 separation performances of composite membranes of 6FDA-based polyimides with a polar group[J]. J Membr Sci, 2003, 211(1):41-49.

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