Preparation and properties of flower-like polyimide/polyimide and thermally rearranged mixed matrix membranes
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摘要: 混合基质膜(MMMs)由于制备方法简单，综合性能优异，在气体分离领域具有较强的竞争力。为提高填料与聚合物基体间的相容性，本文采用溶剂热法制备的花状聚酰亚胺(PI)为填料，以含羟基聚酰亚胺为基体，采用原位聚合法，经热酰亚胺化和热重排反应制备出了一系列花状聚酰亚胺/聚酰亚胺及其热重排(TR)混合基质膜。化学结构相似的聚酰亚胺填料和基体间形成了良好的界面相容性，赋予混合基质膜较为优异的气体分离性能。当花状PI的掺杂量为3wt%时，混合基质膜TR-3wt%的晶面间距达到0.64 nm，对H2、CO2、O2、CH4和N2的气体渗透率相对于TR膜分别提高了61.36%、67.90%、81.58%、37.88%和51.72%，且O2/N2的选择性为5.49，接近2015年上限；CO2/CH4的选择性为22.36，超过2008年Robeson上限。因此，该策略将为高性能MMMs的界面设计工程提供一定参考。Abstract: Mixed matrix membranes (MMMs) show strong competitiveness in the field of gas separation due to their simple preparation method and excellent comprehensive performance. In order to improve the compatibility between fillers and polymer matrix, a series of flower-like polyimide(PI)/polyimide and their thermally rearranged (TR) mixed matrix membranes were prepared by in situ polymerization method, using the flower-like polyimide synthesized from solvothermal method as fillers and the hydroxyl-containing polyimide as matrix, followed by thermal imidization and thermal rearrangement treatment. Because the polyimide filler and matrix can form better compatibility because of their similar chemical structures, the mixed matrix membranes showed superior gas separation performance. When the doping content of the flower-like PI particles was 3wt%, the mixed matrix membrane TR-3wt% exhibited a d-spacing value of 0.64 nm, and the gas permeabilities of H2, CO2, O2, CH4 and N2 were respectively increased by 61.36%, 67.90%, 81.58%, 37.88%, and 51.72% compared to the TR membrane. Moreover, the ideal selectivity of O2/N2 was 5.49, close to the 2015 Upper Limit. The selectivity of CO2/CH4 reached 22.36, exceeding the 2008 Robeson Upper Limit. Therefore, this design strategy will provide a certain reference for the interface design of MMMs.
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Key words:
- Mixed matrix membrane /
- Flower-like polyimide /
- Thermal rearrangement /
- Gas separation /
- Interface
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图 1 (a) 混合基质膜的制备流程；(b) 热转化历程；(c) 气体渗透测试装置
Figure 1. (a) Preparation process of MMMs; (b) Thermal conversion process; (c) Gas permeability test unit
图 2 红外光谱图 (a) 花状PI(6FAP-PMDA)和HPI(6FAP-6FDA)混合基质膜；(b) 热重排的花状PI(6FAP-PMDA)和TR混合基质膜
Figure 2. FTIR spectra (a) Flower-like PI(6FAP-PMDA) and HPI(6FAP-6FDA) MMMs; (b) Rearranged flower-like PI(6FAP-PMDA) and TR MMMs
图 3 (a) HPI混合基质膜的表观照片；SEM图：(b) 花状PI(6FAP-PMDA)颗粒；(c) HPI(6FAP-6FDA), ×10 k；(d) HPI-1wt%, ×10 k；(e) HPI-5wt%, ×10 k；(f) HPI-10wt%, ×10 k； (g) HPI-10wt%, ×1 k
Figure 3. (a) Digital photos of HPI MMMs; SEM images: (b) Flower-like PI(6FAP-PMDA) particles; (c) HPI(6FAP-6FDA), ×10 k; (d) HPI-1wt%, ×10 k; (e) HPI-5wt%, ×10 k; (f) HPI-10wt%, ×10 k; (g) HPI-10wt%, ×1 k
图 4 应力-应变曲线 (a) HPI混合基质膜；(b) TR混合基质膜；(c) 不同热重排温度制得的混合基质膜
Figure 4. Stress-strain curves (a) HPI MMMs; (b) TR MMMs; (c) MMMs obtained from different TR temperatures
图 8 TR混合基质膜的气体分离性能 (a) O2/N2对O2渗透率；(b) CO2/CH4对CO2渗透率
Figure 8. Gas separation performance of TR MMMs (a) O2/N2 vs. O2 permeability, (b) CO2/CH4 vs. CO2 permeability
表 1 TR混合基质膜的气体分离性能
Table 1. Gas separation performance of TR MMMs
Samples Gas permeabilitya/(10−14 mol·m−1·s−1·Pa−1) Ideal selectivityb H2 CO2 O2 CH4 N2 CO2/N2 O2/N2 CO2/CH4 H2/N2 TR 44.2 40.6 8.9 2.2 1.9 20.90 4.59 18.36 22.76 TR-0.25wt% 49.2 45.5 10.2 2.6 2.2 20.58 4.62 17.41 22.26 TR-0.5wt% 55.8 52.1 11.7 2.8 2.4 21.30 4.78 18.51 22.84 TR-1wt% 63.6 59.5 13.3 2.9 2.7 21.66 4.84 20.18 23.15 TR-3wt% 71.4 68.2 16.2 3.0 2.9 23.13 5.49 22.36 24.20 TR-5wt% 57.3 55.3 12.5 2.6 2.6 21.91 4.71 20.91 21.63 TR-10wt% 51.5 47.5 9.9 2.4 2.3 20.85 4.34 19.42 22.63 Note: a The experimental conditions were 30°C and the constant pressure was 0.01 MPa (0.1 atm), b Ideal selectivity is obtained by the ratio of the permeability of the two gases. 
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