Preparation and Gas Separation Properties of Polymers of Intrinsic Microporosity PIM-1 Based Thermally Induced Rigid Membranes
LU Yunhua1, HAO Jican1, LI Lin2, SONG Jing2, XIAO Guoyong1, HU Zhizhi1, WANG Tonghua2
1 School of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051; 2 School of Chemical Engineering, Dalian University of Technology, Dalian 116024
Abstract: Firstly,5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethylspirobisindane was synthesized from catechol and acetone as the raw materials. Then, the intrinsically microporous polymer PIM-1 was prepared from a dioxane-forming reaction between the home-made 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethylspirobisindane and 2,3,5,6-tetrafluoroterephthalonitrile. The PIM-1 polymer membranes were thermally treated at 300 ℃,350 ℃ and 400 ℃ for 1 h under the N2 atmosphere, respectively. The structures and properties of the tetrahydroxyl compound, PIM-1 polymer and the PIM-1 based thermally induced rigid membranes were characterized by nuclear magnetic resource (NMR), gel permeation chromatography (GPC), differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR), X-ray diffraction (XRD) and scanning electron microscope (SEM), and the gas separation properties of these membranes were also measured with five kinds of pure gases, including H2, O2, N2, CO2 and CH4. These experimental results showed that the obtained PIM-1 exhibited good thermal properties with the glass transition temperature (Tg) of 340 ℃ and the thermal decomposition temperature (Td) of 503 ℃. The gas permeabilities of the resultant PIM-1 based thermally induced rigid membranes were further improved by controlling the processing temperature. After the thermal treatment at 300 ℃, the permeabilities of H2, O2, N2, CO2 and CH4 of the thermally induced rigid membranes were 2 865 Barrer,1 071 Barrer,298 Barrer,7 070 Barrer and 495 Barrer, separately. Furthermore, with the temperature increasing, the permeabilities of these gas separation membranes were decreased, but the selectivity was improved. For the PIM-1-400 membrane, the selectivity of CO2/CH4 was 18.51.
鲁云华, 郝继璨, 李琳, 宋晶, 肖国勇, 胡知之, 王同华. 自具微孔聚合物PIM-1基热致刚性膜材料的制备及气体分离性能[J]. 材料导报, 2018, 32(16): 2876-2881.
LU Yunhua, HAO Jican, LI Lin, SONG Jing, XIAO Guoyong, HU Zhizhi, WANG Tonghua. Preparation and Gas Separation Properties of Polymers of Intrinsic Microporosity PIM-1 Based Thermally Induced Rigid Membranes. Materials Reports, 2018, 32(16): 2876-2881.
1 Zhang B, Wang T H, Hu L H, et al. Advance in polyimide-based carbon membranes for gas separation[J].Membrane Science and Technology,2007,27(5):97(in Chinese). 张兵,王同华,呼立红,等.聚酰亚胺基气体分离炭膜的进展[J].膜科学与技术,2007,27(5):97. 2 Chen X, Wang Y, Jiang L. Research progress of preparation me-thods of CO2-favored permeation membranes[J]. Chemical Journal of Chinese Universities,2013,34(2):249(in Chinese). 陈曦,王耀,江雷.CO2选择性透过膜材料的制备[J].高等学校化学学报,2013,34(2):249. 3 Wu X M, Zhang Q G, Zhu A M, et al. Advances in structure controls and modifications of PIMs membranes for gas separation[J]. Progress in Chemistry,2014,26(7):1214(in Chinese). 吴新妹,张秋根,朱爱梅,等.自具微孔高分子气体分离膜的结构调控与改性研究[J].化学进展,2014,26(7):1214. 4 Xu S J, Liang L Y, Li B Y, et al. Research progress on microporous organic polymers[J]. Progress in Chemistry,2011,23(10):2085(in Chinese). 徐叔军,梁丽芸,李步怡,等.有机微孔聚合物研究进展[J].化学进展,2011,23(10):2085. 5 Budd P M, Mckeown N B, Fritsch D. Polymers of intrinsic microporosity (PIMs): High free volume polymers for membrane applications[J]. Macromolecular Symposia,2006,245(1):403. 6 Carta M,Malpass-Evans R,Croad M,et al. An efficient polymer molecular sieve for membrane gas separations[J]. Science,2013,339(6117):303. 7 Chen Y R, Chen L H, Chang K S, et al. Structural characteristics and transport behavior of triptycene-based PIMs membranes: A combination study using ab initio calculation and molecular simulations[J]. Journal of Membrane Science,2016,514:114. 8 Fritsch D, Bengtson G, Carta M, et al. Synthesis and gas per-meation properties of spirobischromane-based polymers of intrinsic microporosity[J]. Macromolecular Chemistry & Physics,2011,212(11):1137. 9 Budd P M, McKeown N B, Ghanem B S, et al. Gas permeation parameters and other physicochemical properties of a polymer of intrinsic microporosity: Polybenzodioxane PIM-1[J]. Journal of Membrane Science,2008,325(2):851. 10 Thomas S, Pinnau I, Du N, et al. Pure-and mixed-gas permeation properties of a microporous spirobisindane-based ladder polymer (PIM-1)[J]. Journal of Membrane Science,2009,333(1-2):125. 11 Budd P M, Elabas E S, Ghanem B S,et al. Solution-processed, organophilic membrane derived from a polymer of intrinsic microporo-sity[J]. Advanced Materials,2004,16(16):456. 12 Du N Y, Robertson G P, Pinnau I, et al. Copolymers of intrinsic microporosity based on 2,2',3,3'-Tetrahydroxy-1,1'-dinaphthyl[J]. Macromolecular Rapid Communications,2009,30(8):584. 13 Zhao H Y, Xie Q, Ding X L, et al. High performance post-modified polymers of intrinsic microporosity (PIM-1) membranes based on multivalent metal ions for gas separation[J]. Journal of Membrane Science,2016,514:305. 14 McDonald T O, Akhtar R, Lau C H, et al. Using intermolecular interactions to crosslink PIM-1 and modify its gas sorption properties[J]. Journal of Materials Chemistry A,2015,3(9):4855. 15 Budd P M, Elabas E S, Ghanem B S, et al. Solution-processed, organophilic membrane derived from a polymer of intrinsic microporosity[J]. Advanced Materials,2004,16(16):456. 16 Li F Y, Chung T S. Physical aging, high temperature and water vapor permeation studies of UV-rearranged PIM-1 membranes for advanced hydrogen purification and production[J]. International Journal of Hydrogen Energy,2013,38(23):9786. 17 Yong W F, Chung T. Mechanically strong and flexible hydrolyzed polymers of intrinsic microporosity (PIM-1) membranes[J]. Journal of Polymer Science Part B: Polymer Physics,2017,55:344. 18 Bushell A F, Attfield M P, Mason C R, et al. Gas permeation parameters of mixed matrix membranes based on the polymer of intrinsic microporosity PIM-1 and the zeolitic imidazolate framework ZIF-8[J]. Journal of Membrane Science,2013,427(1):48. 19 Ahn J, Chung W J, Pinnau I, et al. Gas transport behavior of mixed-matrix membranes composed of silica nanoparticles in a polymer of intrinsic microporosity (PIM-1)[J]. Journal of Membrane Science,2010,346(2):280 20 Gonciaruk A, Althumayri K, Harrison W J,et al. PIM-1/graphene composite: A combined experimental and molecular simulation study[J]. Microporous & Mesoporous Materials,2015,209:126. 21 Khan M M,Filiz V,Bengtson G,et al. Enhanced gas permeability by fabricating mixed matrix membranes of functionalized multiwalled carbon nanotubes and polymers of intrinsic microporosity[J]. Journal of Membrane Science,2013,436:109. 22 Yong W F, Li F Y, Xiao Y C, et al. Molecular engineering of PIM-1/matrimid blend membranes for gas separation[J]. Journal of Membrane Science,2012,407-408:47. 23 Li F Y, Xiao Y, Chung T S, et al. High-performance thermally self-cross-linked polymer of intrinsic microporosity (PIM-1) membranes for energy development[J]. Macromolecules,2012,45(3):1427. 24 Lu Y H, Hao J C, Li L, et al. Synthesis and gas separation properties of thermally induced rigid membranes[J]. Acta Polymerica Sinica,2016(8):1145(in Chinese). 鲁云华,郝继璨,李琳,等.热致刚性膜材料的合成与气体分离性能研究[J].高分子学报,2016(8):1145. 25 Bjork J A, Brostrom M L, Whitcomb D R. Molecular and supramolecular structure of 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane, tetrahydrofuran solvate[J]. Journal of Chemical Crystallography,1997,27(4):223. 26 Robeson L M. The upper bound revisited[J]. Journal of Membrane Science,2008,320:390.
渝公网安备50019002502923号 版权所有：《材料导报》编辑部
2018, Vol. 32 
