Organic support-supported benzimidazole and amide-linked polymer membranes, methods of making, and h2 / co2 separation applications

Abstract

The application relates to an organic support-carrying benzimidazole and amide connected polymer film, a preparation method and H2 / CO2 separation application; a polymer film main chain is alternately composed of rigid benzimidazole units and flexible amide segments, the film takes an organic film as a support, and a branched polyethylene imine is introduced into the main chain. The organic support is pretreated by the polyethylene imine, the support micropore defects are repaired, and the monomer diffusion difference is made up based on interface adsorption control, the benzimidazole and amide connected polymer film is synthesized through a one-step interface polymerization method, an H2 selective gas transmission channel is effectively constructed, the film area is enlarged through a silicone rubber coating post-processing process, the micropore defects generated in the enlargement process of the film are made up, and high-efficiency H2 / CO2 separation in a pressurized environment is realized. The film has excellent separation performance under 150 o C and 5~30 bar, and has large-scale preparation potential.

Description

Technical Field

[0001] This invention belongs to the field of membrane separation materials technology, and relates to a benzimidazole and amide-linked polymer film supported on an organic support, its preparation method, scale-up, and application; suitable for H2 / CO2 mixed gas separation at 5~30 bar. Specifically, it relates to a benzimidazole and amide-linked polymer film supported on an organic support, its preparation method, and its application in H2 / CO2 separation. Background Technology

[0002] Membrane separation technology has become one of the most promising H2 purification technologies due to its advantages such as small footprint, low energy consumption, and simple operation. However, this technology still faces significant challenges in practical applications: (1) the size difference between hydrogen (molecular dynamic diameter 2.89 Å) and carbon dioxide (3.30 Å) is extremely small, making it difficult for traditional membrane materials to achieve effective separation through size sieving; (2) harsh conditions such as high temperature, high pressure, and water vapor in industrial environments exacerbate the performance degradation of membrane materials. To date, there are no commercially available membrane products for large-scale H2 / CO2 separation scenarios worldwide, and existing H2 / CO2 separation membranes have not reached the ideal level for industrial applications in terms of key performance indicators such as selectivity and permeability.

[0003] As the core of membrane separation technology, the selection of membrane materials is crucial. Polymers, as an important class of separation membrane materials, play a vital role in the research process of H2 purification membranes. In recent years, membranes prepared from covalent organic frameworks (COFs) [X. Tian, ​​H.Huan, K. Zhang, et al. Building Unit Engineering Toward COF Membranes with Controlled Stacking for H2 Purification. Advanced Materials. 2025; 37(32):2504622.] have shown attractive H2 / CO2 separation performance at room temperature and pressure. Simplifying the preparation method and further improving its H2 purification efficiency under high temperature and high pressure conditions will become a key direction for breakthrough research in this field. In contrast, classic polyimide (PI) materials [S. Cong, Y. Yuan, J. Wang, et al. Network polyimidemembranes prepared by interfacial polymerization for hot H2 purification. AIChE Journal. 2022;69(4): e17983.] and polyamide (PA) materials [H. An, MG Shin, CH Yoo, et al. Expanding interfacial polymerization for gas separation beyond waterpurification. Journal of Membrane Science. 2025;713: 123331.] have shown better high-temperature and high-pressure resistance. The application of polybenzimidazole (PBI) materials in H2 / CO2 separation has further enhanced the H2 purification potential of membranes under high temperature and high pressure environments. However, the inherent rigid structure of PBI materials limits the feasibility of increasing gas permeability by reducing film thickness.Therefore, interfacial polymerization (IP) technology has been used to prepare low-thickness polymer membranes containing benzimidazole linker groups [MX Shan, XL Liu, XRWang, et al. Facile manufacture of porous organic framework membranes for precombustion CO2 capture. SCIENCE ADVANCES. 2018;4(9): eaau1698.]. This method not only effectively improves the processability of the material, but also ensures that the prepared membrane maintains excellent H2 / CO2 separation performance under high temperature and high pressure conditions.

[0004] Currently reported benzimidazole-linked polymer membranes are mainly divided into two categories based on the structural differences of the selective layer linking units. One category is benzimidazole-imine-linked polymer (BIILP) membranes [Guo Z, Cong S, Luan L, et al.Molecular‐scale hybrid membranes: Metal‐oxo cluster crosslinked benzimidazole‐linked polymer membranes for superior H2 purification. AIChEJournal. 2023;69(11): e18226.], and the other category is benzimidazole-amide-linked polymer (BIALP) membranes [X.Yan, T. Song, M. Li, et al. Sub-micro porous thin polymer membranes for discriminating H2 and CO2. Nature Communications. 2024; 15: 628.]. Both types of materials are covalently linked network materials, characterized by the synergistic effect of rigid benzimidazole rings and flexible imine (or amide) segments. This unique architecture can effectively form intrinsic and transient pores, thus endowing the materials with excellent H2 selective separation performance. It is worth noting that existing studies on BIALP and BIILP membranes have all used inorganic supports. The application of organic supports (such as polyacrylonitrile, polysulfone, and polyethersulfone) can not only significantly reduce production costs and promote large-scale preparation, but also achieve precise control of membrane structure through surface functional group modification. Existing research shows that BIALP membranes supported on polyacrylonitrile supports have achieved an H2 permeability of 738 GPU and an H2 / CO2 selectivity of 62.0 under ambient pressure, but their pressure resistance has not been systematically evaluated [X. Yan, T. Song, M. Li, et al. Sub-micro porous thin polymermembranes for discriminating H2 and CO2. Nature Communications. 2024; 15:628.]. Based on current research progress, organically supported BIALP membranes show great promise for hydrogen purification, but there is a pressing need to improve their H2 purification performance under pressurized conditions. Enhancing the structural stability and separation efficiency of materials under pressurized conditions through synergistic optimization of molecular structure design and preparation processes remains a key scientific challenge in this field. Summary of the Invention

[0005] The purpose of this invention is to provide a benzimidazole and amide-linked polymer film supported on an organic support, its preparation method, scale-up, and applications, particularly for H2 / CO2 separation under pressures of 5–30 bar. By pretreating the organic support with polyethyleneimine to repair microporous defects and compensating for monomer diffusion differences based on interfacial adsorption control, a benzimidazole and amide-linked polymer film is synthesized via a one-step interfacial polymerization method. This effectively constructs a gas transport channel with H2 selectivity, achieving efficient H2 / CO2 separation under pressure. The film can withstand pressures up to 150 bar. o It exhibits excellent separation performance at C and 5–30 bar, showing potential for large-scale preparation. The structure of the benzimidazole and amide-linked polymer film prepared by support pretreatment and one-step interfacial polymerization is shown in the figure below. Figure 1 As shown, branched PEI, m-phenylenediamine, and 3,3'-diaminobenzidine in the aqueous phase undergo polymerization with 1,3,5-benzyltricarboxyl chloride at the interface to generate a highly cross-linked benzimidazole and amide-linked polymer film.

[0006] The technical solution of the present invention is as follows:

[0007] An organic support-supported benzimidazole and amide linked polymer film, wherein the main chain is composed of alternating rigid benzimidazole units and flexible amide segments, the film uses an organic film as a support and introduces branched polyethyleneimine into the main chain.

[0008] The present invention discloses a method for preparing a benzimidazole and amide-linked polymer film supported on an organic support, comprising the following steps:

[0009] 1): Take out the organic support that has been soaked and stored in ultrapure water, fix it in the membrane forming assembly, and then dry it in an oven at 40~80 ℃ for 10~20 min;

[0010] 2): Immerse the upper surface of the support obtained in the first step in a polyethyleneimine aqueous solution with a mass percentage concentration of 0.1~0.5 wt%, and let it stand in a constant temperature and humidity chamber for 10~20 min to allow the solution to fully wet the support; then take it out, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious liquid droplets on the surface.

[0011] 3): Immerse the upper surface of the polyethyleneimine-containing support obtained in the second step in an aqueous solution of m-phenylenediamine and 3,3'-diaminobenzidine mixed in a mass ratio, and let it stand in a constant temperature and humidity chamber for 10-20 minutes to allow the solution to fully wet the support; then take it out, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious droplets on the surface.

[0012] 4): The upper surface of the support obtained in step 3 is immersed in an organic solution containing 1,3,5-benzenetricarboxyl chloride with a mass percentage concentration of 0.2~0.6 wt%. Polyethyleneimine, m-phenylenediamine and 3,3'-diaminobenzidine on the upper surface of the support undergo interfacial polymerization reaction with 1,3,5-benzenetricarboxyl chloride on the support surface for 1~60 min.

[0013] 5): Take the benzimidazole and amide-linked polymer film prepared in step 4 out of the constant temperature and humidity chamber, quickly put it into the forced-air drying oven, heat-treat and cyclize it, and then take it out; then put it into the fume hood to cool, and obtain a benzimidazole and amide-linked polymer film supported on an organic support with a black brown surface.

[0014] The organic support in step 1) includes one of polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyamide, nylon or polyvinylidene fluoride.

[0015] In step 3), the aqueous solution of the mixture of intermediate phenylenediamine and 3,3'-diaminobenzidine has a mass percentage concentration of intermediate phenylenediamine of 0.5-1.5 wt%; the aqueous solution of the mixture of intermediate phenylenediamine and 3,3'-diaminobenzidine has a mass percentage concentration of 3,3'-diaminobenzidine of 0.5-1.5 wt%; and the mass ratio of intermediate phenylenediamine to 3,3'-diaminobenzidine is 3:1 to 1:3.

[0016] The organic solvent used in step 4) is one of n-hexane, benzene, toluene, and n-heptane.

[0017] The heat treatment temperature in step 5) is 100~150 ℃.

[0018] The temperature and humidity chamber is 25~60 ℃ and 30%~50%.

[0019] The present invention discloses a method for preparing an organic support-supported benzimidazole and amide-linked polymer film. The method involves coating the upper surface of the organic support-supported benzimidazole and amide-linked polymer film obtained in step five with a two-component addition-type silicone rubber. A silicone rubber solution is prepared according to a mass ratio of main agent: curing agent: solvent of 10:1:100~20:1:400. After the solvent evaporates naturally, the film is placed in a vacuum oven for curing, resulting in a silicone rubber-coated organic support-supported benzimidazole and amide-linked polymer film.

[0020] The method for preparing a benzimidazole and amide-linked polymer film supported on an organic support uses one of the following solvents: water, n-hexane, benzene, toluene, ethanol, propanol, isopropanol, or acetone. The two-component addition-cure silicone rubber is Dow Corning DC184 or Dow SE1700. The film is cured in a vacuum oven at 45–70 °C and 0.03–0.06 MPa for 10–15 h.

[0021] The specific explanation is as follows:

[0022] This invention discloses a benzimidazole and amide-linked polymer film supported on an organic support, wherein the main chain consists of alternating rigid benzimidazole units and flexible amide segments. Unlike previously reported benzimidazole and amide-linked polymer films, this film uses a low-cost organic membrane as the support and incorporates branched polyethyleneimine into the main chain, thereby significantly enhancing the interfacial bonding between the support and the selective layer. This film exhibits excellent H2 / CO2 separation performance in the test pressure range of 5–30 bar, which is significantly superior to previously reported polymer membranes.

[0023] The fixing device of the present invention can use a common quick-install welding flange blind plate set or other common film forming components.

[0024] Typically prepared membranes still exhibit an H2 / CO2 selectivity greater than 4.7 at a test pressure of 5 bar, such as membranes with an area of ​​17.9 cm². 2 The membrane was fabricated at that time. To increase the gas flux to meet industrial application requirements, the membrane area needed to be further increased. When the test pressure was 5 bar, if the H2 / CO2 selectivity was less than 4.7, a post-coating process was required to compensate for the micropore defects generated during the membrane area increase process, ensuring the membrane's H2 / CO2 separation capability under pressure. For example, the membrane area could be increased to 56.6 cm². 2 In the process of scaling up the membrane area, we can also utilize the silicone rubber post-coating technique. This involves coating the surface of the benzimidazole and amide-linked polymer film supported on the organic support obtained in step five with a silicone rubber solution prepared at a mass ratio of 10:1:100~20:1:400 (main agent: curing agent: solvent). After the solvent evaporates naturally, the film is placed in a vacuum oven at 45~70 ℃ and 0.03~0.06 MPa for 10~15 hours to obtain a silicone rubber-coated organic support-supported benzimidazole and amide-linked polymer film. The solvent is one of water, n-hexane, benzene, toluene, ethanol, propanol, isopropanol, or acetone.

[0025] Unlike the two-layer structure of benzimidazole and amide-linked polymer films supported by organic supports, the silicone rubber-coated organic support benzimidazole and amide-linked polymer films contain a three-layer structure. Figure 2 The membrane consists of a bottom support layer, a middle selector layer, and an uppermost ultra-thin, non-porous silicone rubber coating. The silicone rubber coating and the selector layer are primarily bonded through hydrogen bonds and physical interlocking. The silicone rubber coating can compensate for micropore defects caused by the increased membrane area, thereby improving the flux and yield of the mixed gas treated by the membrane while slightly sacrificing permeability and H2 / CO2 selectivity, thus better meeting the needs of industrial applications.

[0026] The organically supported benzimidazole and amide-linked polymer membrane of this invention is used for the separation of H2 / CO2 mixed gases in a 5-30 bar pressurized system. The polymer membrane, possessing both intrinsic and transient pores, preferentially allows molecules with smaller molecular dynamics (e.g., hydrogen molecules with a molecular dynamics diameter of 2.89 Å) to pass through, while significantly hindering the diffusion of larger gas molecules (e.g., carbon dioxide, nitrogen, and methane molecules with kinetic diameters of 3.30, 0.364, and 0.380 Å, respectively) between the intrinsic pores and the polymer chains. The fabricated membrane can be used for H2 purification under high pressure, at 150... o At 30 bar, the H2 / CO2 selectivity is 16.5, with a corresponding H2 permeability of 53.7 GPU. The benzimidazole and amide-linked polymer membrane supported on a silicone rubber-coated organic support effectively increases the membrane area by 15 times, significantly improving H2 flux and making it suitable for H2 / CO2 separation in 5-20 bar pressurized systems. This invention offers a low-cost, simple, and short preparation cycle. The disclosed one-step interfacial polymerization method for preparing both the organic support-supported benzimidazole and amide-linked polymer film and the silicone rubber-coated organic support-supported benzimidazole and amide-linked polymer membrane exhibits high gas permeability, high selectivity, good stability, and is easily scalable under pressure, potentially meeting the needs of practical industrial conditions and applications.

[0027] The benzimidazole and amide-linked polymer films supported by organic supports and the benzimidazole and amide-linked polymer films coated with silicone rubber supported by organic supports disclosed in this invention differ from existing benzimidazole and amide-linked polymer films and other polymer films, as their use of supports and reaction mechanisms are innovative. The films are prepared by interfacial polymerization of m-phenylenediamine and 3,3'-diaminobenzidine with 1,3,5-benzenetriformyl chloride. The microenvironment of the membrane interface is controlled by parameters such as reaction temperature, reaction time, monomer ratio, monomer concentration, support type, and membrane preparation process. Pretreatment with polyethyleneimine aqueous solution repairs microporous defects in the organic support and improves the hydrophilicity of the support surface. Surface adsorption allows for uniform distribution of the aqueous monomers on the support surface, thereby fully utilizing the monomer polymerization and crosslinking capabilities, creating more H2 selective channels, and effectively improving the separation performance (permeability and selectivity) and stability (30 bar high-pressure stability and water vapor resistance) of the benzimidazole and amide-linked polymer films supported by organic supports. Furthermore, by enlarging the membrane area through a silicone rubber coating post-processing technique, the micropore defects generated during the membrane expansion process are compensated, significantly improving the flux and yield of treated gas permeating the membrane and enhancing the feasibility of the membrane for industrial applications.

[0028] Specifically, the benzimidazole and amide-linked polymer film supported on the organic support is a novel organic polymer linked by benzimidazole and amide bonds, possessing a highly cross-linked network structure. The introduction of PEI and a suitable MPD to DAB mass ratio provide optimized interfacial adsorption sites for DAB, fully leveraging its cross-linking advantages to construct more H2 selective channels, thereby improving the membrane's separation capability. Furthermore, the addition of PEI not only improves the hydrophilicity of the support surface but also participates in the polymerization reaction, enhancing the bonding force between the selective layer and the support layer, thus improving the membrane's stability.

[0029] This invention has the following advantages:

[0030] First, the upper surface of the support was immersed in an aqueous solution of polyethyleneimine and left to stand in a constant temperature and humidity chamber to allow the pretreatment solution to fully penetrate the support and coat its surface. The modified upper surface of the support was then immersed in an aqueous solution of m-phenylenediamine and 3,3'-diaminobenzidine and left to stand in a constant temperature and humidity chamber to ensure full contact between the aqueous solution and the support. Subsequently, the upper surface of the support was immersed in an organic solution containing 1,3,5-benzenetriformyl chloride, where the two monomers polymerized on the support surface to obtain a thin polymer membrane. The resulting polymer membrane was then heat-treated in a forced-air drying oven. The synergistic effect of the rigid benzimidazole unit and the flexible amide segment maintains the high separation capacity of the polymer membrane supported by the organic support while significantly improving its pressure resistance stability.

[0031] Organic polymers are low-cost, readily functionalizable, and scalable support materials. A one-step interfacial polymerization method was used to construct a polymer network. By introducing branched polyethyleneimine and optimizing preparation parameters, the microstructure and polymer chain stacking of the polymer membrane were controlled, enhancing size sieving, promoting the transfer of molecules with smaller molecular dynamics, and significantly hindering the passage of gas molecules with larger dynamic diameters. The resulting benzimidazole and amide-linked polymer membrane contained both inherent pores and transient pores generated by polymer chain perturbations, exhibiting excellent H2 purification capabilities and outstanding pressure resistance. The benzimidazole and amide-linked polymer membrane prepared by this method showed high gas permeability, high selectivity, and good tolerance. At 150°C... o At C, 30 bar, the H2 / CO2 ratio is 16.5, and the corresponding H2 permeability is 53.7 GPU, which has the potential to achieve efficient H2 purification under actual industrial conditions.

[0032] To meet the requirements for gas throughput and yield in practical industrial applications, and to further increase the membrane area, a benzimidazole and amide-linked polymer membrane supported on an organic support coated with silicone rubber was prepared. This membrane significantly improved the flux of the mixed gas through the membrane and maintained an H2 / CO2 selectivity greater than 10 at a high pressure of 20 bar, demonstrating promising prospects for industrial applications. Attached Figure Description

[0033] Figure 1 Schematic diagram of the structure for preparing benzimidazole and amide-linked polymer films via support pretreatment and one-step interfacial polymerization.

[0034] Figure 2 A schematic diagram of the membrane structure and H2 / CO2 separation of a benzimidazole and amide-linked polymer membrane supported on a silicone rubber-coated organic support.

[0035] Figure 3 The image shows the Fourier transform infrared spectrum of the corresponding powder in Example 1 of this invention.

[0036] Figure 4 This is a scanning electron microscope image of the benzimidazole and amide-linked polymer film supported on a polyethyleneimine pretreated polyethersulfone (20 kDa) support in Example 4 of the present invention.

[0037] Figure 5 In Example 4 of this invention, a benzimidazole and amide-linked polymer film supported on a polyethyleneimine-pretreated polyethersulfone (20 kDa) support was subjected to constant temperature (150 °C). o C) Gas separation performance under varying cyclic pressure (5~30 bar).

[0038] Figure 6 The figures show a comparison of the H2 / CO2 separation performance (10-20 bar) of the benzimidazole and amide-linked polymer membrane supported on the polyethyleneimine pretreated polyethersulfone (20 kDa) support in Example 4 of this invention with that of previously reported polymer membranes, as well as a comparison of the H2 / CO2 separation performance with other previously reported membranes at a feed pressure of 30 bar. Detailed Implementation

[0039] The preferred embodiments of the present invention will be described in detail below. Although the preferred embodiments of the present invention are specifically described below, it should be understood that the present invention can be implemented in various forms and should not be limited to the embodiments set forth herein.

[0040] Example 1

[0041] 1): The 50 kDa polysulfone support that was soaked and stored in ultrapure water was taken out, fixed in the membrane forming assembly, and then dried in an oven at 80°C for 15 min;

[0042] 2): Immerse the upper surface of the support obtained in the first step in a 0.2 wt% aqueous solution of polyethyleneimine, and let it stand in a constant temperature (40 ℃) and constant humidity (30%) chamber for 20 min to allow the solution to fully wet the support. Then remove it, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious droplets on the surface;

[0043] 3): The upper surface of the polyethyleneimine-containing support obtained in step 2 was immersed in an aqueous solution of m-phenylenediamine (1 wt%) and 3,3'-diaminobenzidine (1 wt%) mixed in a 1:1 mass ratio, and left to stand in a constant temperature and humidity chamber for 20 min to allow the solution to fully wet the support. Then it was removed, left to stand, and dried in a constant temperature and humidity chamber until no obvious droplets remained on the surface.

[0044] 4): The upper surface of the support obtained in step 3 was immersed in a 1,3,5-benzenetricarboxyl chloride-n-hexane solution with a mass percentage concentration of 0.2 wt%. Polyethyleneimine, m-phenylenediamine and 3,3'-diaminobenzidine on the upper surface of the support underwent interfacial polymerization reaction with 1,3,5-benzenetricarboxyl chloride on the support surface for 30 min.

[0045] 5): Remove the benzimidazole and amide-linked polymer membrane prepared in step 4 from the constant temperature and humidity chamber and quickly place it in a 150°C environment. o After heat treatment and cyclization in a C-type forced-air oven, the film was removed and then cooled in a fume hood to obtain a polysulfone (50 kDa) supported benzimidazole and amide-linked polymer film (film area 17.9 cm²). 2 The effective test area is 1.33 cm². 2 ). Figure 3 The Fourier transform infrared spectrum of the corresponding powder confirmed the successful synthesis of the benzimidazole-amide linked polymer. The characteristic peaks at 1605 cm⁻¹ (C=N stretching vibration) and 1243 cm⁻¹ (CN stretching vibration) confirmed the successful construction of the benzimidazole ring structure. Simultaneously, the C=O stretching vibration peak at 1656 cm⁻¹ (amide I band) and the NH bending vibration peak at 1534 cm⁻¹ (amide II band) indicated the formation of the amide bond.

[0046] Testing of benzimidazole and amide-linked polymer films supported on polysulfone (50 kDa) supports at 150 °C o C. The permeation performance and selectivity at 5 bar (all pressures in this patent refer to gauge pressure, and transmembrane pressure difference = gauge pressure - 1) are: P H2=50.0 GPU, P CO2 =8.39 GPUs, P H2 / P CO2 =6.05.

[0047] Example 2

[0048] 1): Take out the 50 kDa polyethersulfone support that has been soaked and stored in ultrapure water, fix it in the film-forming assembly, and then dry it in an oven at 80°C for 15 min;

[0049] 2): Immerse the upper surface of the support obtained in the first step in a 0.2 wt% aqueous solution of polyethyleneimine, and let it stand in a constant temperature (40 ℃) and constant humidity (30%) chamber for 20 min to allow the solution to fully wet the support. Then remove it, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious droplets on the surface;

[0050] 3): The upper surface of the polyethyleneimine-containing support obtained in step 2 was immersed in an aqueous solution of m-phenylenediamine (1 wt%) and 3,3'-diaminobenzidine (1 wt%) mixed in a 1:1 mass ratio, and left to stand in a constant temperature and humidity chamber for 20 min to allow the solution to fully wet the support. Then it was removed, left to stand, and dried in a constant temperature and humidity chamber until no obvious droplets remained on the surface.

[0051] 4): The upper surface of the support obtained in step 3 was immersed in a 1,3,5-benzenetricarboxyl chloride-n-hexane solution with a mass percentage concentration of 0.2 wt%. Polyethyleneimine, m-phenylenediamine and 3,3'-diaminobenzidine on the upper surface of the support underwent interfacial polymerization reaction with 1,3,5-benzenetricarboxyl chloride on the support surface for 30 min.

[0052] 5): Remove the benzimidazole and amide-linked polymer membrane prepared in step 4 from the constant temperature and humidity chamber and quickly place it in a 150°C environment. o After heat treatment and cyclization in a C-type forced-air oven, the film was removed and then cooled in a fume hood to obtain a polyethersulfone (50 kDa) supported benzimidazole and amide-linked polymer film (film area 17.9 cm²). 2 The effective test area is 1.33 cm². 2 ).

[0053] Testing of benzimidazole and amide-linked polymer films supported on polyethersulfone (50 kDa) supports at 150 °C o C, The permeability and selectivity of the H2 / CO2 mixed gas at 5 bar are: P H2 =36.3 GPUs, P CO2 =3.41 GPUs, P H2 / P CO2 =11.0.

[0054] Example 3

[0055] 1): Take out the 20 kDa polyethersulfone support that has been soaked and stored in ultrapure water, fix it in the film-forming assembly, and then dry it in an oven at 80°C for 15 min;

[0056] 2): Immerse the upper surface of the support obtained in the first step in a 0.2 wt% aqueous solution of polyethyleneimine, and let it stand in a constant temperature (40 ℃) and constant humidity (30%) chamber for 20 min to allow the solution to fully wet the support. Then remove it, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious droplets on the surface;

[0057] 3): The upper surface of the polyethyleneimine-containing support obtained in step 2 was immersed in an aqueous solution of m-phenylenediamine (1.5 wt%) and 3,3'-diaminobenzidine (0.5 wt%) mixed in a 3:1 mass ratio, and left to stand in a constant temperature and humidity chamber for 20 min to allow the solution to fully wet the support. Then it was removed, left to stand, and dried in a constant temperature and humidity chamber until no obvious droplets remained on the surface.

[0058] 4): The upper surface of the support obtained in step 3 was immersed in a 1,3,5-benzenetricarboxyl chloride-n-hexane solution with a mass percentage concentration of 0.2 wt%. Polyethyleneimine, m-phenylenediamine and 3,3'-diaminobenzidine on the upper surface of the support underwent interfacial polymerization reaction with 1,3,5-benzenetricarboxyl chloride on the support surface for 30 min.

[0059] 5): Remove the benzimidazole and amide-linked polymer membrane prepared in step 4 from the constant temperature and humidity chamber and quickly place it in a 150°C environment. o After heat treatment and cyclization in a C-type forced-air oven, the film was removed and then cooled in a fume hood to obtain a polyethersulfone (20 kDa) supported benzimidazole and amide-linked polymer film (film area 17.9 cm²). 2 The effective test area is 1.33 cm². 2 ).

[0060] Testing of benzimidazole and amide-linked polymer films supported on polyethersulfone (20 kDa) supports at 150 °C o C. The permeability and selectivity at 5 bar are: P H2 =40.6 GPUs, P CO2 =2.87 GPU, P H2 / P CO2 =14.8.

[0061] Example 4

[0062] 1): Take out the 20 kDa polyethersulfone support that has been soaked and stored in ultrapure water, fix it in the film-forming assembly, and then dry it in an oven at 80°C for 15 min;

[0063] 2): Immerse the upper surface of the support obtained in the first step in a 0.2 wt% aqueous solution of polyethyleneimine, and let it stand in a constant temperature (40 ℃) and constant humidity (30%) chamber for 20 min to allow the solution to fully wet the support. Then remove it, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious droplets on the surface;

[0064] 3): The upper surface of the polyethyleneimine-containing support obtained in step 2 was immersed in an aqueous solution of m-phenylenediamine (1 wt%) and 3,3'-diaminobenzidine (1 wt%) mixed in a 1:1 mass ratio, and left to stand in a constant temperature and humidity chamber for 20 min to allow the solution to fully wet the support. Then it was removed, left to stand, and dried in a constant temperature and humidity chamber until no obvious droplets remained on the surface.

[0065] 4): The upper surface of the support obtained in step 3 was immersed in a 1,3,5-benzenetricarboxyl chloride-n-hexane solution with a mass percentage concentration of 0.2 wt%. Polyethyleneimine, m-phenylenediamine and 3,3'-diaminobenzidine on the upper surface of the support underwent interfacial polymerization reaction with 1,3,5-benzenetricarboxyl chloride on the support surface for 30 min.

[0066] 5): Remove the benzimidazole and amide-linked polymer membrane prepared in step 4 from the constant temperature and humidity chamber and quickly place it in a 150°C environment. o After heat treatment and cyclization in a C-type forced-air oven, the film was removed and then cooled in a fume hood to obtain a polyethersulfone (20 kDa) supported benzimidazole and amide-linked polymer film (film area 17.9 cm²). 2 The effective test area is 1.33 cm². 2 ).

[0067] The morphology of the membrane is as follows Figure 4 As shown, the membrane surface exhibits a nanoscale wrinkled structure, which likely originates from the stress and heat accumulation caused by the rapid condensation of the aqueous monomer (MPD / DAB) and the organic monomer (TMC) at the interface. Furthermore, this membrane achieves an ultrathin selective layer with a thickness of only 51 nm. A constant temperature of 150 °C was maintained. o C. Permeability and selectivity of H2 / CO2 mixed gas under varying circulating pressure (5~30 bar), such as Figure 5As shown. It was found that reducing the pressure from 30 bar to 5 bar completely restored the membrane's permeability and H2 / CO2 selectivity to their initial states, and no significant performance fluctuations were observed during a 200-hour stability test. Specific performance at different pressures is listed below. The H2 / CO2 separation performance of this membrane is compared with reported polymer membranes (10–20 bar) and with other reported membranes at a feed pressure of 30 bar. Figure 6 As shown, the membrane exhibits superior H2 / CO2 separation performance across various pressure ranges, standing out among numerous polymer membranes in terms of overall performance. Even under high pressure conditions of 30 bar, the membrane's separation performance is still significantly better than most membrane materials. These performance results indicate that this material has excellent industrial applicability and can meet the practical needs of industrial H2 purification over a wide pressure range.

[0068] Testing of benzimidazole and amide-linked polymer films supported on polyethersulfone (20 kDa) supports at 150 °C o The permeability and selectivity of the H2 / CO2 mixed gas at C and different test pressures (5~30 bar) are as follows: 5 bar, P H2 =61.8 GPUs, P CO2 =1.70 GPU, P H2 / P CO2 =36.4.10 bar, P H2 =59.8 GPUs, P CO2 =1.90 GPU, P H2 / P CO2 =32.5.15 bar, P H2 =57.7 GPUs, P CO2 =2.10 GPU, P H2 / P CO2 =27.9.20 bar, P H2 =55.8 GPU, P CO2 =2.40 GPU, P H2 / P CO2 =23.4.25 bar, P H2 =55.2 GPU, P CO2 =2.70 GPU, P H2 / P CO2 =20.3.30 bar, P H2 =53.7 GPUs, P CO2 =3.30 GPU, P H2 / P CO2 =16.5.

[0069] Example 5

[0070] 1): Take out the 20 kDa polyethersulfone support that has been soaked and stored in ultrapure water, fix it in the film-forming assembly, and then dry it in an oven at 80°C for 15 min;

[0071] 2): Immerse the upper surface of the support obtained in the first step in a 0.2 wt% aqueous solution of polyethyleneimine, and let it stand in a constant temperature (40 ℃) and constant humidity (30%) chamber for 20 min to allow the solution to fully wet the support. Then remove it, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious droplets on the surface;

[0072] 3): The upper surface of the polyethyleneimine-containing support obtained in step 2 was immersed in an aqueous solution of m-phenylenediamine (0.5 wt%) and 3,3'-diaminobenzidine (1.5 wt%) mixed in a mass ratio of 1:3, and left to stand in a constant temperature and humidity chamber for 20 min to allow the solution to fully wet the support. Then it was removed, left to stand, and dried in a constant temperature and humidity chamber until no obvious droplets remained on the surface.

[0073] 4): The upper surface of the support obtained in step 3 was immersed in a 1,3,5-benzenetricarboxyl chloride-n-hexane solution with a mass percentage concentration of 0.2 wt%. Polyethyleneimine, m-phenylenediamine and 3,3'-diaminobenzidine on the upper surface of the support underwent interfacial polymerization reaction with 1,3,5-benzenetricarboxyl chloride on the support surface for 30 min.

[0074] 5): Remove the benzimidazole and amide-linked polymer membrane prepared in step 4 from the constant temperature and humidity chamber and quickly place it in a 150°C environment. o After heat treatment and cyclization in a C-type forced-air oven, the film was removed and then cooled in a fume hood to obtain a polyethersulfone (20 kDa) supported benzimidazole and amide-linked polymer film (film area 17.9 cm²). 2 The effective test area is 1.33 cm². 2 ).

[0075] Testing of benzimidazole and amide-linked polymer films supported on polyethersulfone (20 kDa) supports at 150 °C o C. The permeability and selectivity at 5 bar are: P H2 =124 GPUs, P CO2 =27.7 GPUs, P H2 / P CO2 =4.50.

[0076] Example 6

[0077] 1): Take out the 20 kDa polyethersulfone support that has been soaked and stored in ultrapure water, fix it in the film-forming assembly, and then dry it in an oven at 80°C for 15 min;

[0078] 2): Immerse the upper surface of the support obtained in the first step in a 0.2 wt% aqueous solution of polyethyleneimine, and let it stand in a constant temperature (40 ℃) and constant humidity (30%) chamber for 20 min to allow the solution to fully wet the support. Then remove it, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious droplets on the surface;

[0079] 3): The upper surface of the polyethyleneimine-containing support obtained in step 2 was immersed in an aqueous solution of m-phenylenediamine (1 wt%) and 3,3'-diaminobenzidine (1 wt%) mixed in a 1:1 mass ratio, and left to stand in a constant temperature and humidity chamber for 20 min to allow the solution to fully wet the support. Then it was removed, left to stand, and dried in a constant temperature and humidity chamber until no obvious droplets remained on the surface.

[0080] 4): The upper surface of the support obtained in step 3 was immersed in a 1,3,5-benzenetricarboxyl chloride-n-hexane solution with a mass percentage concentration of 0.2 wt%. Polyethyleneimine, m-phenylenediamine and 3,3'-diaminobenzidine on the upper surface of the support underwent interfacial polymerization reaction with 1,3,5-benzenetricarboxyl chloride on the support surface for 30 min.

[0081] 5): Remove the benzimidazole and amide-linked polymer membrane prepared in step 4 from the constant temperature and humidity chamber and quickly place it in 100°C. o After heat treatment and cyclization in a C-type forced-air oven, the film was removed and then cooled in a fume hood to obtain a polyethersulfone (20 kDa) supported benzimidazole and amide-linked polymer film (film area 17.9 cm²). 2 The effective test area is 1.33 cm². 2 ).

[0082] Testing of benzimidazole and amide-linked polymer films supported on polyethersulfone (20 kDa) supports at 150 °C o C. The permeability and selectivity at 5 bar are: P H2 =46.8 GPUs, P CO2 =6.12 GPUs, P H2 / P CO2 =7.71.

[0083] Example 7

[0084] 1): Take out the 20 kDa polyethersulfone support that has been soaked and stored in ultrapure water, fix it in the film-forming assembly, and then dry it in an oven at 80°C for 15 min;

[0085] 2): Immerse the upper surface of the support obtained in the first step in a 0.2 wt% aqueous solution of polyethyleneimine, and let it stand in a constant temperature (40 ℃) and constant humidity (30%) chamber for 20 min to allow the solution to fully wet the support. Then remove it, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious droplets on the surface;

[0086] 3): The upper surface of the polyethyleneimine-containing support obtained in step 2 was immersed in an aqueous solution of m-phenylenediamine (1 wt%) and 3,3'-diaminobenzidine (1 wt%) mixed in a 1:1 mass ratio, and left to stand in a constant temperature and humidity chamber for 20 min to allow the solution to fully wet the support. Then it was removed, left to stand, and dried in a constant temperature and humidity chamber until no obvious droplets remained on the surface.

[0087] 4): The upper surface of the support obtained in step 3 was immersed in a 1,3,5-benzenetricarboxyl chloride-n-hexane solution with a mass percentage concentration of 0.2 wt%. Polyethyleneimine, m-phenylenediamine and 3,3'-diaminobenzidine on the upper surface of the support underwent interfacial polymerization reaction with 1,3,5-benzenetricarboxyl chloride on the support surface for 30 min.

[0088] 5): Remove the benzimidazole and amide-linked polymer membrane prepared in step 4 from the constant temperature and humidity chamber and quickly place it in a 120°C environment. o After heat treatment and cyclization in a C-type forced-air oven, the film was removed and then cooled in a fume hood to obtain a polyethersulfone (20 kDa) supported benzimidazole and amide-linked polymer film (film area 17.9 cm²). 2 The effective test area is 1.33 cm². 2 ).

[0089] Testing of benzimidazole and amide-linked polymer films supported on polyethersulfone (20 kDa) supports at 150 °C o C. The permeability and selectivity at 5 bar are: P H2 =60.3 GPUs, P CO2 =3.54 GPU, P H2 / P CO2 =17.2.

[0090] Example 8

[0091] 1): Take out the 20 kDa polyethersulfone support that has been soaked and stored in ultrapure water, fix it in the film-forming assembly, and then dry it in an oven at 80°C for 15 min;

[0092] 2): Immerse the upper surface of the support obtained in the first step in a 0.2 wt% aqueous solution of polyethyleneimine, and let it stand in a constant temperature (40 ℃) and constant humidity (30%) chamber for 20 min to allow the solution to fully wet the support. Then remove it, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious droplets on the surface;

[0093] 3): The upper surface of the polyethyleneimine-containing support obtained in step 2 was immersed in an aqueous solution of m-phenylenediamine (1 wt%) and 3,3'-diaminobenzidine (1 wt%) mixed in a 1:1 mass ratio, and left to stand in a constant temperature and humidity chamber for 20 min to allow the solution to fully wet the support. Then it was removed, left to stand, and dried in a constant temperature and humidity chamber until no obvious droplets remained on the surface.

[0094] 4): The upper surface of the support obtained in step 3 was immersed in a 1,3,5-benzenetricarboxyl chloride-n-hexane solution with a mass percentage concentration of 0.2 wt%. Polyethyleneimine, m-phenylenediamine and 3,3'-diaminobenzidine on the upper surface of the support underwent interfacial polymerization reaction with 1,3,5-benzenetricarboxyl chloride on the support surface for 30 min.

[0095] 5): The benzimidazole and amide-linked polymer film prepared in step 4 is removed from the constant temperature and humidity chamber and quickly placed in a 150 ℃ forced-air drying oven for heat treatment and cyclization before being removed. It is then placed in a fume hood for cooling to obtain a benzimidazole and amide-linked polymer film supported on a polyethersulfone (20 kDa) support.

[0096] 6): The surface of the benzimidazole and amide-linked polymer film supported on the polyethersulfone (20 kDa) support obtained in step 5 is coated with a silicone rubber solution prepared at a mass ratio of 10:1:100 (Dow Corning DC184 main agent: Dow Corning DC184 curing agent: n-hexane). After the n-hexane evaporates naturally, the film is placed in a vacuum oven at 60 °C and 0.03 MPa for 12 h to cure, resulting in a silicone rubber-coated polyethersulfone (20 kDa) support-supported benzimidazole and amide-linked polymer film (the area of ​​the prepared film is 56.6 cm²). 2 The effective test area is 19.6 cm². 2 ).

[0097] Testing of benzimidazole and amide-linked polymer films supported on silicone rubber-coated polyethersulfone (20 kDa) supports at 150 °C o The permeability and selectivity of the H2 / CO2 mixed gas under C and different test pressures are: 5 bar, P H2 =43.6 GPUs, P CO2 =6.46 GPU, P H2 / P CO2 =6.75.10 bar, PH2 =43.7 GPUs, P CO2 =7.23 GPU, P H2 / P CO2 =6.06.

[0098] Example 9

[0099] 1): The 50 kDa polyacrylonitrile support, which was stored in ultrapure water, was taken out, fixed in the membrane forming assembly, and then dried in an oven at 40 °C for 20 min.

[0100] 2): Immerse the upper surface of the support obtained in the first step in a 0.1 wt% aqueous solution of polyethyleneimine, and let it stand in a constant temperature (25 ℃) and constant humidity (50%) chamber for 10 min to allow the solution to fully wet the support. Then remove it, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious droplets on the surface;

[0101] 3): The upper surface of the polyethyleneimine-containing support obtained in step 2 was immersed in an aqueous solution of m-phenylenediamine (1.5 wt%) and 3,3'-diaminobenzidine (0.5 wt%) mixed in a 3:1 mass ratio, and left to stand in a constant temperature and humidity chamber for 10 min to allow the solution to fully wet the support. Then it was removed, left to stand, and dried in a constant temperature and humidity chamber until no obvious droplets remained on the surface.

[0102] 4): The upper surface of the support obtained in step 3 is immersed in a 1,3,5-benzenetricarboxyl chloride-n-heptane solution with a mass percentage concentration of 0.6 wt%. Polyethyleneimine, m-phenylenediamine and 3,3'-diaminobenzidine on the upper surface of the support undergo interfacial polymerization reaction with 1,3,5-benzenetricarboxyl chloride on the support surface for 1 min.

[0103] 5): The benzimidazole and amide-linked polymer film prepared in step 4 is removed from the constant temperature and humidity chamber and quickly placed in a 150 ℃ forced-air drying oven for heat treatment and cyclization before being removed. It is then cooled in a fume hood to obtain a benzimidazole and amide-linked polymer film supported on a polyacrylonitrile (50 kDa) support.

[0104] 6): The surface of the benzimidazole and amide-linked polymer film supported on the polyacrylonitrile (50 kDa) support obtained in step 5 is coated with a silicone rubber solution prepared at a mass ratio of 20:1:400 (Dow Corning DC184 main agent: Dow Corning DC184 curing agent: ethanol). After the ethanol evaporates naturally, the film is placed in a vacuum oven at 70 °C and 0.05 MPa for 10 h to cure, resulting in a silicone rubber-coated polyacrylonitrile (50 kDa) support-supported benzimidazole and amide-linked polymer film (film area 56.6 cm²). 2 The effective test area is 19.6 cm².2 ).

[0105] Testing of benzimidazole and amide-linked polymer films supported on silicone rubber-coated polyacrylonitrile (50 kDa) supports at 150 °C o C, the permeability and selectivity of the H2 / CO2 mixed gas at 5 bar are: P H2 =152 GPUs, P CO2 =30.6 GPUs, P H2 / P CO2 =4.97.

[0106] Example 10

[0107] 1): Take out the 50 kDa polyacrylonitrile support that has been soaked and stored in ultrapure water, fix it in the membrane forming assembly, and then dry it in an oven at 60 °C for 10 min;

[0108] 2): Immerse the upper surface of the support obtained in the first step in a 0.5 wt% aqueous solution of polyethyleneimine, and let it stand in a constant temperature (60 ℃) and constant humidity (40%) chamber for 15 min to allow the solution to fully wet the support. Then remove it, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious droplets on the surface;

[0109] 3): The upper surface of the polyethyleneimine-containing support obtained in step 2 was immersed in an aqueous solution of m-phenylenediamine (1.5 wt%) and 3,3'-diaminobenzidine (0.5 wt%) mixed in a 3:1 mass ratio, and left to stand in a constant temperature and humidity chamber for 15 min to allow the solution to fully wet the support. Then it was removed, left to stand, and dried in a constant temperature and humidity chamber until no obvious droplets remained on the surface.

[0110] 4): The upper surface of the support obtained in step 3 was immersed in a 1,3,5-benzenetricarboxyl chloride-n-heptane solution with a mass percentage concentration of 0.4 wt%. Polyethyleneimine, m-phenylenediamine and 3,3'-diaminobenzidine on the upper surface of the support underwent interfacial polymerization with 1,3,5-benzenetricarboxyl chloride on the support surface for 60 min.

[0111] 5): The benzimidazole and amide-linked polymer film prepared in step 4 is removed from the constant temperature and humidity chamber and quickly placed in a 150 ℃ forced-air drying oven for heat treatment and cyclization before being removed. It is then cooled in a fume hood to obtain a benzimidazole and amide-linked polymer film supported on a polyacrylonitrile (50 kDa) support.

[0112] 6): The surface of the benzimidazole and amide-linked polymer film supported on the polyacrylonitrile (50 kDa) support obtained in step 5 is coated with a silicone rubber solution prepared at a mass ratio of 15:1:300 (Dow SE1700 main agent: Dow SE1700 curing agent: ethanol). After the ethanol evaporates naturally, the film is placed in a vacuum oven at 45 °C and 0.06 MPa for 15 h to cure, resulting in a silicone rubber-coated polyacrylonitrile (50 kDa) support-supported benzimidazole and amide-linked polymer film (film area 56.6 cm²). 2 The effective test area is 19.6 cm². 2 ).

[0113] Testing of benzimidazole and amide-linked polymer films supported on silicone rubber-coated polyacrylonitrile (50 kDa) supports at 150 °C o C, the permeability and selectivity of the H2 / CO2 mixed gas at 5 bar are: P H2 =81.3 GPUs, P CO2 =16.2 GPUs, P H2 / P CO2 =5.03.

[0114] Example 11

[0115] 1): Take out the 20 kDa polyethersulfone support that has been soaked and stored in ultrapure water, fix it in the film-forming assembly, and then dry it in an oven at 80°C for 15 min;

[0116] 2): Immerse the upper surface of the support obtained in the first step in a 0.2 wt% aqueous solution of polyethyleneimine, and let it stand in a constant temperature (40 ℃) and constant humidity (30%) chamber for 20 min to allow the solution to fully wet the support. Then remove it, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious droplets on the surface;

[0117] 3): The upper surface of the polyethyleneimine-containing support obtained in step 2 was immersed in an aqueous solution of m-phenylenediamine (1.5 wt%) and 3,3'-diaminobenzidine (0.5 wt%) mixed in a 3:1 mass ratio, and left to stand in a constant temperature and humidity chamber for 20 min to allow the solution to fully wet the support. Then it was removed, left to stand, and dried in a constant temperature and humidity chamber until no obvious droplets remained on the surface.

[0118] 4): The upper surface of the support obtained in step 3 was immersed in a 1,3,5-benzenetricarboxyl chloride-n-hexane solution with a mass percentage concentration of 0.2 wt%. Polyethyleneimine, m-phenylenediamine and 3,3'-diaminobenzidine on the upper surface of the support underwent interfacial polymerization reaction with 1,3,5-benzenetricarboxyl chloride on the support surface for 30 min.

[0119] 5): The benzimidazole and amide-linked polymer film prepared in step 4 is removed from the constant temperature and humidity chamber and quickly placed in a 150 ℃ forced-air drying oven for heat treatment and cyclization before being removed. It is then placed in a fume hood for cooling to obtain a benzimidazole and amide-linked polymer film supported on a polyethersulfone (20 kDa) support.

[0120] 6): The surface of the benzimidazole and amide-linked polymer film supported on the polyethersulfone (20 kDa) support obtained in step 5 is coated with a silicone rubber solution prepared at a mass ratio of 10:1:100 (Dow Corning DC184 main agent: Dow Corning DC184 curing agent: n-hexane). After the n-hexane evaporates naturally, the film is placed in a vacuum oven at 60 °C and 0.03 MPa for 12 h to cure, resulting in a silicone rubber-coated polyethersulfone (20 kDa) support-supported benzimidazole and amide-linked polymer film (the area of ​​the prepared film is 56.6 cm²). 2 The effective test area is 19.6 cm². 2 ).

[0121] Testing of benzimidazole and amide-linked polymer films supported on silicone rubber-coated polyethersulfone (20 kDa) supports at 150 °C o The permeability and selectivity of the H2 / CO2 mixed gas under C and different test pressures are as follows: 10 bar, P H2 =14.4 GPUs, P CO2 =1.27 GPU, P H2 / P CO2 =11.1.15 bar, P H2 =14.4 GPUs, P CO2 =1.72 GPU, P H2 / P CO2 =8.43.20 bar, P H2 =12.8 GPU, P CO2 =1.86 GPU, P H2 / P CO2 =7.05.

[0122] Example 12

[0123] 1): Take out the 20 kDa polyethersulfone support that has been soaked and stored in ultrapure water, fix it in the film-forming assembly, and then dry it in an oven at 80°C for 15 min;

[0124] 2): Immerse the upper surface of the support obtained in the first step in a 0.2 wt% aqueous solution of polyethyleneimine, and let it stand in a constant temperature (40 ℃) and constant humidity (30%) chamber for 20 min to allow the solution to fully wet the support. Then remove it, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious droplets on the surface;

[0125] 3): The upper surface of the polyethyleneimine-containing support obtained in step 2 was immersed in an aqueous solution of m-phenylenediamine (1.5 wt%) and 3,3'-diaminobenzidine (0.5 wt%) mixed in a 3:1 mass ratio, and left to stand in a constant temperature and humidity chamber for 20 min to allow the solution to fully wet the support. Then it was removed, left to stand, and dried in a constant temperature and humidity chamber until no obvious droplets remained on the surface.

[0126] 4): The upper surface of the support obtained in step 3 was immersed in a 1,3,5-benzenetricarboxyl chloride-n-hexane solution with a mass percentage concentration of 0.2 wt%. Polyethyleneimine, m-phenylenediamine and 3,3'-diaminobenzidine on the upper surface of the support underwent interfacial polymerization with 1,3,5-benzenetricarboxyl chloride on the support surface for 20 min.

[0127] 5): The benzimidazole and amide-linked polymer film prepared in step 4 is removed from the constant temperature and humidity chamber and quickly placed in a 150 ℃ forced-air drying oven for heat treatment and cyclization before being removed. It is then placed in a fume hood for cooling to obtain a benzimidazole and amide-linked polymer film supported on a polyethersulfone (20 kDa) support.

[0128] 6): The surface of the benzimidazole and amide-linked polymer film supported on the polyethersulfone (20 kDa) support obtained in step 5 is coated with a silicone rubber solution prepared at a mass ratio of 10:1:100 (Dow Corning DC184 main agent: Dow Corning DC184 curing agent: n-hexane). After the n-hexane evaporates naturally, the film is placed in a vacuum oven at 60 °C and 0.03 MPa for 12 h to cure, resulting in a silicone rubber-coated polyethersulfone (20 kDa) support-supported benzimidazole and amide-linked polymer film (the area of ​​the prepared film is 56.6 cm²). 2 The effective test area is 19.6 cm². 2 ).

[0129] Testing of benzimidazole and amide-linked polymer films supported on silicone rubber-coated polyethersulfone (20 kDa) supports at 150 °C o The permeability and selectivity of the H2 / CO2 mixed gas under C and different test pressures are as follows: 10 bar, P H2 =32.8 GPUs, P CO2 =1.90 GPU, P H2 / P CO2 =17.4.15 bar, P H2 =29.8 GPUs, P CO2 =2.24 GPU, P H2 / P CO2 =13.8.20 bar, P H2 =27.2 GPUs, P CO2=2.33 GPUs, P H2 / P CO2 =11.7.

[0130] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the requirements of the present invention should be included within the protection scope of the present invention.

[0131] This invention discloses and proposes an organically supported benzimidazole and amide-linked polymer film, its preparation method, scale-up, and applications. Those skilled in the art can implement these methods by appropriately modifying conditions and procedures, based on the content of this document. Although the methods and preparation techniques of this invention have been described through preferred embodiments, those skilled in the art can clearly modify or recombine the methods and techniques described herein without departing from the content, spirit, and scope of this invention to achieve the final preparation technique. It is particularly important to note that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included within the spirit, scope, and content of this invention.

Claims

1. A method for preparing a benzimidazole and amide-linked polymer film supported on an organic support, characterized in that, The process steps include: 1): Take out the organic support that has been soaked and stored in ultrapure water, fix it in the membrane forming assembly, and then dry it in an oven at 40~80 ℃ for 10~20 min; 2): Immerse the upper surface of the support obtained in the first step in a polyethyleneimine aqueous solution with a mass percentage concentration of 0.1~0.5 wt%, and let it stand in a constant temperature and humidity chamber for 10~20 min to allow the solution to fully wet the support; then take it out, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious liquid droplets on the surface. 3): Immerse the upper surface of the polyethyleneimine-containing support obtained in the second step in an aqueous solution of m-phenylenediamine and 3,3'-diaminobenzidine mixed in a mass ratio, and let it stand in a constant temperature and humidity chamber for 10-20 minutes to allow the solution to fully wet the support; then take it out, let it stand, and dry it in a constant temperature and humidity chamber until there are no obvious droplets on the surface. 4): The upper surface of the support obtained in step 3 is immersed in an organic solution containing 1,3,5-benzenetricarboxyl chloride with a mass percentage concentration of 0.2~0.6 wt%. Polyethyleneimine, m-phenylenediamine and 3,3'-diaminobenzidine on the upper surface of the support undergo interfacial polymerization reaction with 1,3,5-benzenetricarboxyl chloride on the support surface for 1~60 min. 5): Take the benzimidazole and amide-linked polymer film prepared in step 4 out of the constant temperature and humidity chamber, quickly put it into the forced-air drying oven, heat-treat and cyclize it, and then take it out; then put it into the fume hood to cool, and obtain a benzimidazole and amide-linked polymer film supported on an organic support with a black brown surface.

2. The method for preparing a benzimidazole and amide-linked polymer film supported on an organic support as described in claim 1, characterized in that, The organic support in step 1) includes one of polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyamide, nylon or polyvinylidene fluoride.

3. The method for preparing a benzimidazole and amide-linked polymer film supported on an organic support as described in claim 1, characterized in that, Step 3) The aqueous solution of the mixture of intermediate phenylenediamine and 3,3'-diaminobenzidine has an intermediate phenylenediamine mass percentage concentration of 0.5~1.5 wt%; the aqueous solution of the mixture of intermediate phenylenediamine and 3,3'-diaminobenzidine has a 3,3'-diaminobenzidine mass percentage concentration of 0.5~1.5 wt%; and the mass ratio of intermediate phenylenediamine to 3,3'-diaminobenzidine is 3:1~1:

3.

4. The method for preparing a benzimidazole and amide-linked polymer film supported on an organic support as described in claim 1, characterized in that, The organic solvent used in step 4) is one of n-hexane, benzene, toluene, or n-heptane.

5. The method for preparing a benzimidazole and amide-linked polymer film supported on an organic support as described in claim 1, characterized in that, The heat treatment temperature in step 5) is 100~150 ℃.

6. The method for preparing a benzimidazole and amide-linked polymer film supported on an organic support as described in claim 1, characterized in that, The temperature and humidity chamber is 25~60 ℃ and 30%~50%.

7. The method for preparing a benzimidazole and amide-linked polymer film supported on an organic support as described in claim 1, characterized in that, The surface of the benzimidazole and amide-linked polymer film supported by the organic support obtained in step 5 is coated with a two-component addition-type silicone rubber. A silicone rubber solution is prepared according to the mass ratio of main agent: curing agent: solvent of 10:1:100~20:1:

400. After the solvent evaporates naturally, the film is placed in a vacuum oven for curing to obtain a silicone rubber-coated benzimidazole and amide-linked polymer film supported by an organic support.

8. The method for preparing a benzimidazole and amide-linked polymer film supported on an organic support as described in claim 7, characterized in that, The solvent is one of water, n-hexane, benzene, toluene, ethanol, propanol, isopropanol, or acetone; the two-component addition-cure silicone rubber is Dow Corning DC184 or Dow SE1700.

9. The method for preparing a benzimidazole and amide-linked polymer film supported on an organic support as described in claim 7, characterized in that, Place in a vacuum oven at 45~70 ℃ and 0.03~0.06 MPa for 10~15 h to cure.

10. A benzimidazole and amide-linked polymer film supported on an organic support obtained by the preparation method according to claim 1, characterized in that, The main chain is composed of alternating rigid benzimidazole units and flexible amide segments. The film uses an organic membrane as a support and introduces branched polyethyleneimine into the main chain.

Images