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含三甲基苯结构聚酰亚胺气体分离膜的设计合成及其气体分离特性

作者：马臣俣，唐傲，董杰，赵昕，李琇廷，许青松，张清华

单位：东华大学先进纤维材料全国重点实验室，材料科学与工程学院，上海 201620

关键词：聚酰亚胺膜；自由体积；空间位阻；气体分离

DOI号： 10.16159/j.cnki.issn1007-8924.2025.04.009

分类号： TQ051.893

出版年,卷(期):页码： 2025,45(4):86-94

摘要：

聚酰亚胺气体分离膜因其优异的分离性能、力学性能和环境适应性，在气体分离领域引起了广泛关注。然而，目前提高聚酰亚胺气体渗透性能的措施往往会导致选择性和力学性能的大幅下降。因此，协同提高气体分离膜的选择性和渗透性是该领域的一项重要挑战。本研究以二苯酮四酸二酐(BTDA) 与三甲基苯二异氰酸酯(TTDI) 、二苯基甲烷二异氰酸酯(MDI) 进行共聚，通过调控TTDI与MDI的共聚比例，制备了一系列聚酰亚胺气体分离膜。此法避免了“一步法”和“两步法”制备聚酰亚胺气体分离膜所存在的弊端，并且引入三甲基苯结构调控自由体积，从而获得兼顾良好选择性与渗透性的气体分离膜。研究结果表明，当共聚物中TTDI的摩尔分数为80%时，制备的聚酰亚胺分离膜具有良好的热性能，其玻璃化转变温度达到374.60 ℃；此外，该分离膜对O2/N2、CO2/CH4体系表现出良好的分离性能，其对于CO2渗透率为8.02 Barrer，CO2/CH4选择性为57.28，并且在0.3~1.2 MPa气体压力下表现出良好的气体分离稳定性，分离特性优于商业化的P84等产品。

Polyimide gas separation membranes have attracted extensive attention in the gas separation field due to their excellent separation performance, mechanical properties and environmental adaptability. However, current measures to improve the gas permeability of polyimides often lead to significant declines in selectivity and mechanical properties. Therefore, simultaneously enhancing the selectivity and permeability of gas separation membranes is a significant challenge in this field. In this study, copolymerization of diphenylketone tetracarboxylic dianhydride (BTDA) with trimethylbenzene diisocyanate (TTDI) and 4,4′-diphenylmethane diisocyanate (MDI) was conducted. By regulating the copolymerization ratio of TTDI and MDI, a series of polyimide gas separation membranes were prepared. This method avoids the drawbacks of preparing polyimide gas separation membranes by the “one-step method” and the “two-step method”, and introduces the trimethylbenzene structure to regulate the free volume, thereby obtaining gas separation membranes that take into account both good selectivity and permeability. The results showed that when TTDI mole fraction was 80% in the copolymer, the prepared polyimide separation membrane had good thermal performance, with a glass transition temperature of 374.60 ℃. Additionally, this separation membrane exhibited excellent separation performance for O2/N2 and CO2/CH4 systems. Specifically, the CO2 permeability was 8.02 Barrer, and the CO2/CH4 selectivity was 57.28. Moreover, there was no obvious plasticization behavior under gas pressures ranging from 0.3 to 1.2 MPa, and its separation characteristics were superior to commercial products such as P84.

基金项目：

国家自然科学基金（52173196）

作者简介：

马臣俣（1999-），男，江苏无锡人，硕士生，主要研究方向为气体分离膜

参考文献：

[1]Reddy M S B, Ponnamma D, Sadasivuni K K, et al. Carbon dioxide adsorption based on porous materials[J]. RSC Adv, 2021, 11(21): 12658-12681.
[2]Burdyny T, Struchtrup H. Hybrid membrane/cryogenic separation of oxygen from air for use in the oxy-fuel process[J]. Energy， 2010, 35(5): 1884-1897.
[3]王金莲. 吸收CO2的新型化学吸收剂和工艺研究[D].杭州：浙江大学, 2007.
[4]Rogelj J, Elzen M D, Hohne N, et al. Paris agreement climate proposals need a boost to keep warming well below 2 ℃[J]. Nature, 2016, 534: 631-639.
[5]Guivarch C, Mejean A, Pottier A, et al. Social cost of carbon: global duty[J]. Science, 2016, 351 (6278): 1160-1161.
[6]Economides M J, Wood D A. The state of natural gas, [J]. J Nat Gas Sci Eng,2009, 1(1): 1-13.
[7]Bernardo P, Drioli E, Golemme G. Membrane gas separation: A review/state of the art[J]. Ind Eng Chem Res,2009, 48(10): 4638-4663.
[8]Masuelli M A. Ultrafiltration of oil/water emulsions using PVDF/PC blend membranes[J]. Desalin Water Treat, 2015, 53(3): 569-578.
[9]Lyu R, Zhou J, Du Q, et al. Effect of posttreatment on morphology and properties of poly (ethylene-co-vinyl alcohol) microporous hollow fiber via thermally induced phase separation[J]. J Appl Polym Sci, 2007, 104(6): 4106-4112.
[10]Fansuri H, Ismail A F, Widiastuti N, et al. membranes P84/ZCC hollow fiber mixed matrix membrane with PDMS coating to enhance air separation performance[J]. Membranes, 2020, 10(10): 267-280.
[11]Ohya H, Kudryavtsev V V, Semenova S I. Polyimide membranes: Applications, fabrications, and properties[J]. Desalination, 1997, 109(2): 225-233.
[12]Feng L, Iroh J O. Polyimide-b-polysiloxane copolymers: Synthesis and properties[J]. J Inorg Organomet Polym, 2013, 23(3): 477-488.
[13]Gao J, Chung T S. Polyimide hollow fiber membranes and their applications[M]//Amercia: Elsevier, 2021.
[14]Huo G, Xu S, Wu L, et al. Structural engineering on copolyimide membranes for improved gas separation performance[J]. J Membr Sci, 2022, 643: 119989.
[15]Shen Y, Lua A C. Structural and transport properties of BTDA-TDI/MDI co-polyimide (P84) -silica nanocomposite membranes for gas separation[J]. Chem Eng J, 2012, 188:199-209.
[16]Kanehashi S, Sato S, Nagai K. Membrane color and gas permeability of 6FDA-TeMPD polyimide membranes prepared with various membrane preparation protocols[J]. Polym Eng Sci, 2011, 51(12):2360-2369.
[17]Thür R, Lemmens D, Havere D V, et al. Tuning 6FDADABA membrane performance for CO2 removal by physical densification and decarboxylation cross-linking during simple thermal treatment-ScienceDirect[J]. J Membr Sci, 2010, 610:118195.
[18]Ando S, Matsuura T, Sasaki S. Coloration of aromatic polyimides and electronic properties of their source materials[J]. Polym J, 1997, 29(1): 69-76.
[19]Rogan Y, Starannikova L, Ryzhikh V, et al. Synthesis and gas permeation properties of novel spirobisindane-based polyimides of intrinsic microporosity[J]. Polym Chem, 2013, 4(13): 3813-3820.
[20]Guo H, Hu X, Wang Z, et al. Intrinsically microporous polyimides from p-phenylenediamine with fused cyclopentyl substituents for membrane-based gas separation[J]. Sep Purif Technol, 2023,316: 123690.
[21]Li F, Zhang C, Weng Y. Preparation and gas separation properties of triptycene-based microporous polyimide[J]. Macromol Chem Phys, 2019, 220(10): 1900047.
[22]Ahmad M Z, Martin-Gil V, Supinkova T, et al. Novel MMM using CO2 selective SSZ-16 and high-performance 6FDA-polyimide for CO2/CH4 separation[J]. Sep Purif Technol, 2020, 254(1): 117582.
[23]Kim S I, Shin T J, Ree M,et al. Structure and properties of various poly (amic diisopropyl ester-alt-imide)s and their alternating copolyimides[J]. Polymer, 2000, 41(14):5173-5184.
[24]Weber J, Su Q, Antonietti M, et al. Exploring polymers of intrinsic microporosity-microporous, soluble polyamide and polyimide[J]. Macromol Rapid Commum, 2010, 28(18/19): 1871-1876.
[25]Weber J, Du N, Guiver M D. Influence of intermolecular interactions on the observable porosity in intrinsically microporous polymers[J]. Macromolecules, 2011, 44(7): 1763-1767.
[26]McDermott A G, Larsen G S, Budd P M, et al. Structural characterization of a polymer of intrinsic microporosity: X-ray scattering with interpretation enhanced by molecular dynamics simulations[J]. Magn Reson Med, 2010, 44(1): 1135-1144.
[27]Wakita J, Jin S, Shin T J, et al. Analysis of molecular aggregation structures of fully aromatic and semialiphatic polyimide films with synchrotron grazing incidence wide-angle X-ray scattering[J]. Macromolecules, 2010, 43(4): 1930-1941.
[28]Feng Y, Ren J, Li H, et al. Effect of thermal annealing on gas separation performance and aggregation structures of block polyimide membranes[J]. Polymer, 2021, 219:123538.
[29]Jiang Q, Zhang Q, Wu X, et al. Exploring the interfacial phase and pi-pi stacking in aligned carbon nanotube/polyimide nanocomposites[J]. Nanomaterials, 2020,10: 1158.
[30]Wu A X, Lin S, Rodriguez K M, et al. Revisiting group contribution theory for estimating fractional free volume of microporous polymer membranes[J]. J Membr Sci, 2021:119526.
[31]Moon J D, Borjigin H, Liu R, et al. Impact of humidity on gas transport in polybenzimidazole membranes[J]. J Membr Sci, 2021, 639:119758.
[32]Gu, S, Yang G, Ren X Y, et al. The effect of methyl group on the mechanical properties of hydrophobic association hydrogel[J]. J Polym Sci, Part B: Polym Phys, 2018, 56 (22) : 1505-1512.
[33]Wang L, Guo X, Zhang F, et al. Blending and in situ thermally crosslinking of dual rigid polymers for anti-plasticized gas separation membranes[J]. J Membr Sci, 2021,638:119668.
[34]Ma C, Koros W J. Effects of hydrocarbon and water impurities on CO2/CH4 separation performance of ester-crosslinked hollow fiber membranes[J]. J Membr Sci, 2014, 451: 1-9.
[35]Liu G P, Li N W, Stephen J, et al. Molecularly designed stabilized asymmetric hollow fiber membranes for aggressive natural gas separation[J]. Angew Chem, 2016, 128 (44) : 13958-13962.

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