Amide-imine dual-network polymer membrane, preparation method and application of amide-imine dual-network polymer membrane in high-temperature and high-pressure system H2 / CO2 separation

Abstract

The invention discloses an amide-imine dual-network polymer film, a preparation method and an application of the amide-imine dual-network polymer film in H2 / CO2 separation in a high-temperature and high-pressure system. The amide-imine dual-network polymer film coexisting in a crystalline state and an amorphous state is characterized in that crystal polymer structures with same or similar molecular structures exist in an amide-imine connected amorphous polymer film matrix; soaking the support body in an aqueous solution of m-phenylenediamine, taking out the support body, and standing until no obvious liquid drop exists on the surface of the support body; and then soaking in an organic solution of 1, 3, 5-benzoyl chloride and 1, 3, 5-benzenetricarboxaldehyde, and carrying out polymerization reaction on the surface of the support body to obtain the double-network polymer membrane. The polymer membrane shows excellent H2 / CO2 separation performance in a high-temperature and high-pressure system; the method is simple to operate and short in preparation period; the catalyst has high gas permeability, high selectivity and good stability at high temperature and high pressure, is easy for large-scale preparation, and has practical industrial application potential.

Description

Technical Field

[0001] The present invention belongs to the field of membrane separation materials technology and relates to a dual-network polymer membrane comprising coexisting crystalline and amorphous structures, as well as its preparation method and application. The disclosed dual-network polymer membrane comprises an amide-imide-linked amorphous polymer matrix containing crystalline polymer structures with identical or similar molecular structures. The membrane is suitable for use in various temperature and pressure ranges, particularly in the separation of H2 / CO2 mixed gases (including water vapor) at high temperatures (150-250°C) and high pressures (transmembrane pressure differential: 1-11 bar). Background Art

[0002] Membrane separation technology does not involve phase change and has the advantages of simple operation, small footprint and environmental friendliness, and has application potential in gas separation. The performance of separation membranes mainly depends on the membrane material. Polymer membrane materials have low preparation costs, strong processability, and are easy to prepare on a large scale. For polymer membranes, it is most ideal to have both high gas permeability and selectivity. The higher the gas permeability, the smaller the membrane area required to process a certain amount of gas, reducing operating costs; the higher the gas selectivity, the higher the product purity. However, there is a trade-off relationship (trade-off effect) between the gas permeability and selectivity of traditional polymer separation membranes, that is, the gas selectivity of polymer membranes often decreases with increasing gas permeability, which limits the widespread application of polymer membranes.

[0003] Porous organic membrane materials with suitable pore structures and good stability are expected to overcome this constraint. Porous organic polymer materials are porous materials formed by covalently linked organic building blocks. They offer advantages such as large specific surface area, excellent chemical and thermal stability, and well-organized and designable pores, making them a research hotspot for H2 / CO2 separation membranes. Currently, porous organic polymer membranes used for H2 / CO2 separation include intrinsically microporous polymers (PIMs), polyimides (PIs), benzimidazole-linked polymers (BILPs, BIALPs), hypercrosslinked polymers (HCPs), and covalent organic frameworks (COFs). Chung et al. used ultraviolet light to rearrange the PIM-1 polymer chains. At 35°C and 7 bar, the resulting membrane exhibited an H2 / CO2 selectivity of 7.1 and an H2 permeance of 265 barrer (Reference 1). Liu et al. prepared a PI membrane via interfacial polymerization, achieving an H2 / CO2 selectivity of 18.7 and an H2 permeability of 42.3 GPU at 350°C and 1 bar (Reference 2). A polyamide-benzimidazole linked polymer (BIALP) membrane prepared via interfacial polymerization combined with a controlled thermal conversion method achieved an H2 / CO2 selectivity of 35.8 and an H2 permeability of 42 GPU at 150°C and 10 bar (Reference 3). Ansaloni et al. synthesized an HCP membrane on a ceramic tubular support, achieving an H2 permeability greater than 800 GPU but an H2 / CO2 selectivity less than 4.9 (Reference 4). A covalent organic framework membrane (iCON) achieved an H2 permeability of 2600 GPU and an H2 / CO2 selectivity of 22.6 at 150°C and a transmembrane pressure difference of 0.2 bar. However, when the transmembrane pressure difference increased to 1 bar, the H2 / CO2 selectivity dropped sharply to only 1.5 (Reference 5). In recent years, porous polymer membranes have achieved certain breakthroughs in H2 / CO2 separation. However, due to limitations such as the difficulty in precisely controlling the pore structure and pore distribution of membrane materials and the complex membrane manufacturing process, achieving both high gas permeability and high selectivity under high temperature and high pressure conditions remains challenging.

[0004] Literature 1: FYLi, Y. Xiao, YKOng, et al. UV-rearranged PIM-1polymeric membranes for advanced hydrogen purification and production. Advanced Energy Materials. 2012; 2(12): 1456–1466;

[0005] Reference 2: S. Cong, Y. Yuan, J. Wang, et al. Network polyimide membranes prepared by interfacial polymerization for hot H2 purification. AIChE Journal. 2023;69(4):e17983;

[0006] Reference 3: X. Yan, T. Song, M. Li, et al. Sub-micro porous thin polymer membranes for discriminating H2 and CO2. Nature Communications. 2024;15:628;

[0007] Reference 4: L. Ansaloni, E. Louradour, F. Radmanesh, et al. Upscaling polyPOSS-imide membranes for high temperature H2 upgrading. Journal of Membrane Science. 2021;620:118875.

[0008] Reference 5: Y. Ying, M. Tong, S. Ning, et al. Ultrathin two-dimensional membranes assembled by conic covalent organic nanosheets with reduced apertures for gas separation. Journal of the American Chemical Society. 2020;142(9):4472-4480. Summary of the Invention

[0009] The purpose of the present invention is to provide an amide-imide double network polymer separation membrane in which crystalline and amorphous coexist, a preparation method and its application, in particular for use in H2 / CO2 separation under high temperature and high pressure. Based on the difference in monomer reaction activity, an amide-imide double network polymer membrane was synthesized by a one-step interfacial polymerization method to construct a small molecule selective gas permeation channel to achieve high gas permeability and high selectivity. The membrane has a unique structure in which crystalline and amorphous coexist, which has advantages in achieving effective H2 / CO2 separation in harsh environments, in particular in high temperature and high pressure environments. Due to the high rigidity and excellent structural stability of the crystalline polymer network skeleton, the foundation is laid for the temperature and pressure resistance of the double network polymer membrane. The membrane has excellent separation performance at different temperatures (25-250°C, especially high temperature 150-250°C) and pressures (transmembrane pressure difference: 0-11 bar), has the potential for large-scale preparation, and meets the actual industrial conditions for H2 / CO2 separation. The amide-imide double network polymer membrane in which crystalline and amorphous coexist is prepared by a one-step interfacial polymerization method and its structural formula is as follows Figure 1 shown.

[0010] The technical solutions of the present invention are as follows:

[0011] The invention discloses an amide-imide double network polymer membrane with coexistence of crystalline and amorphous states, which refers to an amorphous polymer membrane matrix connected by amide-imide and in which a crystalline polymer structure with the same or similar molecular structure exists.

[0012] The present invention provides a method for preparing a crystalline and amorphous coexisting amide-imide dual network polymer film, the process steps comprising:

[0013] 1) Soaking the support in an aqueous solution of m-phenylenediamine at the reaction temperature for 10 to 60 minutes, allowing the solution to fully penetrate the support, then taking it out, leaving it to stand, and allowing it to dry naturally until no obvious droplets remain on the surface of the support;

[0014] 2) The support obtained in the first step is immersed in an organic solution of 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde preheated to the reaction temperature, and the metaphenylenediamine in the support reacts with the 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxylic acid aldehyde on the surface of the support to obtain an amide-imide double network polymer membrane in which crystalline and amorphous coexist. The reaction time is 1 to 60 minutes.

[0015] 3) The amide-imide double network polymer membrane prepared in the second step, in which crystalline and amorphous coexist, is quickly placed in room temperature ethanol, allowed to stand for 5 to 60 minutes to terminate the reaction, taken out, and naturally dried in a fume hood; thereby obtaining the amide-imide double network polymer membrane in which crystalline and amorphous coexist.

[0016] In the step 1), the support body comprises one of an Al2O3 ceramic sheet, a ceramic tube, polysulfone, polyacrylonitrile, polyimide or a stainless steel support body.

[0017] The mass percentage concentration of m-phenylenediamine in the aqueous solution of m-phenylenediamine in step 1) is 0.01 to 15 wt %, preferably 0.15 to 1.5 wt %.

[0018] The certain temperature in step 1) is a reaction temperature of 5 to 100°C, preferably 60 to 80°C.

[0019] Furthermore, in step 1), the support is preferably left to stand for 10 to 20 minutes after being immersed in the m-phenylenediamine aqueous solution.

[0020] The organic solvent in step 2) includes benzene or toluene.

[0021] The reaction temperature in step 2) is 5-100°C, preferably 60-80°C.

[0022] In the step 2), the mass percentage concentration of the solute in the organic solution containing 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde is 0.01 to 1 wt %, preferably 0.1 to 0.5 wt %.

[0023] In the step 2), the mass ratio of 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the organic solution containing 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxylic acid chloride is 20-80%, preferably 50%.

[0024] In the step 2), the interfacial polymerization reaction time of the m-phenylenediamine aqueous solution and the 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde organic solution on the support surface is preferably 1 to 10 minutes, thereby obtaining an amide-imide double network polymer membrane with coexistence of crystalline and amorphous states.

[0025] The amide-imide dual-network polymer membrane of the present invention, in which crystalline and amorphous coexist, is used to separate H2 / CO2 in a high-temperature and high-pressure system. The prepared dual-network polymer membrane allows the diffusion of molecules with a small kinetic diameter and significantly hinders the migration of molecules with a large kinetic diameter. The prepared membrane is applied to H2 / CO2 separation in a high-temperature and high-pressure environment, particularly at high temperatures of 150-250°C and a transmembrane pressure difference greater than 10 bar. At 150°C and 11 bar, the H2 permeability is 128 GPU and the H2 / CO2 selectivity is 90. The method of the present invention is simple to operate and has a short preparation cycle. The disclosed one-step interfacial polymerization method for preparing a dual-network polymer membrane in which crystalline and amorphous coexist, exhibits high gas permeability, high selectivity, good stability, and is easy to prepare on a large scale at high temperatures and high pressures, meeting actual industrial conditions.

[0026] The amide-imide dual-network polymer membrane, characterized by the coexistence of crystalline and amorphous phases, differs from traditional polyamide membranes and other polymer membranes in that it possesses the same molecular composition but exhibits an innovative structure characterized by the coexistence of crystalline and amorphous phases. The membrane is prepared by interfacial polymerization of m-phenylenediamine, 1,3,5-benzenetricarboxylic acid chloride, and 1,3,5-benzenetricarboxaldehyde. The membrane's microstructure and the stacking of the two polymer networks are controlled by parameters such as reaction temperature, monomer ratio, and membrane-forming process, effectively improving the dual-network polymer membrane's tolerance (temperature and pressure resistance) and separation performance (permeability and selectivity).

[0027] Specifically, the amide-imide dual network polymer membrane, in which crystalline and amorphous coexist, is a new type of porous organic polymer connected by amide and imine bonds, and has a highly cross-linked dual network structure. Among them, the amorphous polymer network easily forms a dense and defect-free separation layer, ensuring the separation performance of the dual network polymer membrane; the crystalline polymer network skeleton is highly rigid and structurally stable, providing a guarantee for the excellent pressure resistance of the dual network polymer membrane. Figure 2 The NMR spectrum shown confirms the existence of both amide and imine networks in the chemical structure of the separation membrane.

[0028] The present invention has the following advantages:

[0029] First, the support is immersed in an aqueous solution of m-phenylenediamine at a constant temperature and allowed to stand until the solution fully penetrates the support. Next, the support is immersed in an organic solution containing 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde. At a constant temperature, the two monomers undergo polymerization on the support surface, forming a dual-network polymer membrane. The resulting dual-network polymer membrane is then placed in ethanol to terminate the reaction. The synergistic effect of the amorphous and crystalline polymer networks maintains the membrane's high permeability and selectivity while significantly improving its pressure resistance.

[0030] Temperature-controlled interfacial polymerization is a method for preparing membrane materials. It is simple and effective, has a fast reaction speed, and produces nanoscale polymer membranes with controllable thickness. The one-step interfacial polymerization method constructs two polymer networks, regulates the microstructure of the polymer membrane and the stacking mode of polymer chains, enhances the size screening effect, promotes the diffusion of molecules with small kinetic diameters (such as H2), and hinders the migration of molecules with large kinetic diameters (such as CO2). The final amide-imide double network polymer membrane contains an amorphous polymer network and a crystalline polymer network, showing a cross-linked network structure and excellent stability. The amide-imide double network polymer membrane prepared by the method has a high gas permeation rate, high selectivity, and good tolerance. At 150°C and 11 bar, the H2 permeability is 128GPU and the H2 / CO2 selectivity is 90, which exceeds the currently reported polymer membranes for H2 / CO2 separation and can be used to achieve effective separation of H2 and CO2 under actual industrial conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The invention discloses a one-step interfacial polymerization method for preparing an amide-imide double network polymer membrane and a structural formula thereof.

[0032] Figure 2 This is a scanning electron microscope image of the polyacrylonitrile support-supported amide-imide double network polymer membrane in Example 2 of the present invention. Figure 3 The stability of the polyacrylonitrile support-supported amide-imide double network polymer membrane in separating H2 / CO2 mixed gases at a test temperature of 150°C and a transmembrane pressure difference of 5 bar in Example 8 of the present invention.

[0033] Figure 4 The amide network-imide network polymer membrane in Example 14 of the present invention 13 C NMR spectrum.

[0034] Figure 5 This is a transmission electron micrograph of the self-supporting crystalline and amorphous coexisting polymer film in Example 14 of the present invention.

[0035] Figure 6 The gas separation performance of the amide-imide dual network polymer membrane in which crystalline and amorphous coexist in Example 14 of the present invention is measured under constant temperature (250° C.) and cyclic multiple pressure changes (1 to 11 bar).

[0036] Figure 7 A comparison chart of the H2 / CO2 mixed gas separation performance of the amide-imide dual network polymer membrane in which crystalline and amorphous coexist in Example 14 of the present invention and reported polymer membranes is shown, where the solid line is the Robeson upper limit of H2 / CO2 of the polymer membrane at different temperatures. DETAILED DESCRIPTION

[0037] Although the preferred embodiments of the present invention are described in detail below, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments described herein.

[0038] Example 1

[0039] Step 1) Weigh 0.3g of m-phenylenediamine at room temperature into a weighing bottle, add 19.7g of deionized water, and sonicate to fully dissolve it, resulting in a 1.5wt% m-phenylenediamine aqueous solution. Place the solution in a preheated oven at 80°C for 30 minutes. Secure the polyacrylonitrile support to the membrane assembly and place it in an 80°C oven for 30 minutes. Then, slowly pour the prepared m-phenylenediamine aqueous solution into the membrane assembly, completely submerging the support. After 10 minutes, discard any excess solution and allow the solution to dry until no visible droplets remain on the surface.

[0040] Step 2) Weigh 0.05g of 1,3,5-benzenetricarboxylic acid chloride and 0.05g of 1,3,5-benzenetricarboxaldehyde into a weighing bottle. Add 19.9g of benzene and sonicate to completely dissolve. Place in a preheated 80°C oven for 30 minutes. Return the membrane assembly, dried in step 1), to an 80°C oven for 30 minutes. Slowly pour the benzene solution into the membrane assembly. The 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the solution will polymerize with the m-phenylenediamine on the surface of the polyacrylonitrile support for 10 seconds.

[0041] Step 3) the film made in step 2 is taken out from baking oven, excess liquid is poured out, a large amount of room temperature ethanol is poured into the membrane assembly rapidly, and left standstill for 10min to terminate the reaction. Pour out ethanol, take the film out from the assembly, and leave it in a fume hood and dry to the film surface solution evaporation completely. The film obtained now is the amide-imide double network polymer film of the crystalline state and amorphous coexistence of the polyacrylonitrile support.

[0042] The permeability and selectivity of the polyacrylonitrile-supported crystalline and amorphous coexisting amide-imide dual network polymer membrane were tested at 150°C and different transmembrane pressure differences (the pressure in this patent refers to the transmembrane pressure difference): 0.5 bar, P H2 =793GPU,P CO2 =39.2GPU,P H2 / P CO2 = 20.2. The porous organic polymer membrane supported on an organic support achieved a breakthrough in pressure resistance under high temperature conditions (greater than 100°C), and the membrane exhibited excellent H2 permeability and H2 / CO2 selectivity.

[0043] Example 2

[0044] Step 1) Weigh 0.3g of m-phenylenediamine at room temperature into a weighing bottle, add 19.7g of deionized water, and sonicate to fully dissolve it, resulting in a 1.5wt% m-phenylenediamine aqueous solution. Place the solution in a preheated oven at 80°C for 30 minutes. Secure the polyacrylonitrile support to the membrane assembly and place it in an 80°C oven for 30 minutes. Then, slowly pour the prepared m-phenylenediamine aqueous solution into the membrane assembly, completely submerging the support. After 30 minutes of undisturbed operation, discard any excess solution and allow the solution to dry until no visible droplets remain on the surface.

[0045] Step 2) Weigh 0.05g of 1,3,5-benzenetricarboxylic acid chloride and 0.05g of 1,3,5-benzenetricarboxaldehyde into a weighing bottle. Add 19.9g of benzene and sonicate to completely dissolve. Place in a preheated 80°C oven for 30 minutes. Return the membrane assembly, dried in step 1), to an 80°C oven for 30 minutes. Slowly pour the benzene solution into the membrane assembly. The 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the solution will polymerize with the m-phenylenediamine on the surface of the polyacrylonitrile support for 10 minutes.

[0046] Step 3) The film prepared in step 2 is taken out of the oven, excess liquid is poured out, and a large amount of room temperature ethanol is quickly poured into the membrane assembly, and the reaction is stopped after standing for 5 minutes. The ethanol is poured out, the membrane is taken out from the assembly, and is left to dry in a fume hood until the solution on the membrane surface evaporates completely. The membrane obtained at this time is an amide-imide double network polymer membrane with coexistence of crystalline and amorphous states supported by a polyacrylonitrile support. The scanning electron microscope of the membrane is as follows: Figure 2 shown.

[0047] The permeability and selectivity of the polyacrylonitrile-supported crystalline and amorphous coexisting amide-imide dual network polymer membrane were tested at 150°C and different transmembrane pressure differences (the pressure in this patent refers to the transmembrane pressure difference): 1 bar, P H2 =73.3GPU,P CO2 =1.06GPU,P H2 / P CO2 =69.0.3bar, P H2 =75.3GPU,P CO2 =2.66GPU,P H2 / P CO2 =28.4.

[0048] Example 3

[0049] Step 1) Weigh 0.01g of m-phenylenediamine at room temperature into a weighing bottle, add 100g of deionized water, and sonicate to fully dissolve it to obtain a 0.01wt% m-phenylenediamine aqueous solution. Place the solution in a preheated oven at 60°C for 30 minutes. Secure the polyacrylonitrile support to the membrane assembly and place it in a 60°C oven for 30 minutes. Then, slowly pour the prepared m-phenylenediamine aqueous solution into the membrane assembly to completely submerge the support. After 60 minutes of undisturbed operation, discard any excess solution and allow the solution to dry until no visible droplets remain on the surface.

[0050] Step 2) Weigh 0.05g of 1,3,5-benzenetricarboxylic acid chloride and 0.05g of 1,3,5-benzenetricarboxaldehyde into a weighing bottle. Add 9.9g of benzene and sonicate to completely dissolve. Place in a preheated 60°C oven for 30 minutes. Return the membrane assembly dried in step 1) to a 60°C oven for 30 minutes. Slowly pour the benzene solution into the membrane assembly. The 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the solution will polymerize with the m-phenylenediamine on the surface of the polyacrylonitrile support for 10 minutes.

[0051] Step 3) step 2 film is taken out from baking oven, excess liquid is poured out, 20mL ethanol is poured in membrane assembly rapidly, leaves standstill 20min, termination reaction.Pour out ethanol, film is taken out from assembly, leaves standstill in fume hood and is dried to film surface solution evaporation complete.The film obtaining now is the crystalline state of polyacrylonitrile support and the amide-imide double network polymer film of amorphous coexistence.

[0052] The permeability and selectivity of the polyacrylonitrile-supported crystalline and amorphous coexisting amide-imide dual network polymer membrane were tested at 150°C and different transmembrane pressure differences (the pressure in this patent refers to the transmembrane pressure difference): 0 bar, P H2 =574GPU,P CO2 =13.2GPU,P H2 / P CO2 =43.5.

[0053] Example 4

[0054] Step 1) Weigh 0.3 g of m-phenylenediamine at room temperature into a weighing bottle, add 199.7 g of deionized water, and sonicate to fully dissolve it to obtain a 0.15 wt% m-phenylenediamine aqueous solution. Place the solution in a preheated oven at 40°C for 30 minutes. Secure the polysulfone support to the membrane assembly and place it in a 40°C oven for 30 minutes. Then, slowly pour the prepared m-phenylenediamine aqueous solution into the membrane assembly to completely submerge the polysulfone support. After 30 minutes of undisturbed operation, discard any excess solution and allow the solution to dry until no visible droplets remain on the surface.

[0055] Step 2) Weigh 0.05g of 1,3,5-benzenetricarboxylic acid chloride and 0.05g of 1,3,5-benzenetricarboxaldehyde into a weighing bottle. Add 99.9g of benzene and sonicate to completely dissolve. Place in a preheated 40°C oven for 30 minutes. Return the membrane assembly dried in step 1) to a 40°C oven for 30 minutes. Slowly pour the benzene solution into the membrane assembly. The 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the solution will polymerize with the m-phenylenediamine on the surface of the polysulfone support for 30 minutes.

[0056] Step 3) step 2 film is taken out from baking oven, excess liquid is poured out, a large amount of room temperature ethanol is poured into membrane assembly rapidly, leaves standstill 5min, termination reaction. Pour out ethanol, film is taken out from assembly, leaves standstill in fume hood and is dried to film surface solution evaporation complete.The film now obtained is the crystalline state of polysulfone support and the amide-imide double network polymer film of amorphous coexistence.

[0057] The permeability and selectivity of the polysulfone support-supported crystalline and amorphous coexisting amide-imide double network polymer membrane at 1 bar (the pressure in this patent refers to the transmembrane pressure difference) and 150°C are as follows: H2 =173GPU,P CO2 =11.1GPU,P H2 / P CO2 =15.6.

[0058] Example 5

[0059] Step 1) 1.5 g of m-phenylenediamine was weighed and placed in a weighing bottle at room temperature. 8.5 g of deionized water was added and thoroughly dissolved by ultrasonication to obtain a 15 wt% m-phenylenediamine aqueous solution. The solution was then stored at 25°C for 30 minutes. A polyacrylonitrile support was secured to the membrane assembly and stored at 25°C for 30 minutes. The prepared m-phenylenediamine aqueous solution was then slowly poured into the membrane assembly to completely submerge the polyacrylonitrile support. After 40 minutes of stagnation, the excess solution was discarded and the membrane was allowed to dry until no visible droplets remained on the surface.

[0060] Step 2) Weigh 0.025g of 1,3,5-benzenetricarboxylic acid chloride and 0.075g of 1,3,5-benzenetricarboxaldehyde into a weighing bottle, add 19.9g of benzene, sonicate to completely dissolve, and store at 25°C for 30 minutes. Slowly pour the benzene solution into the membrane assembly. The 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the solution polymerize with the m-phenylenediamine on the surface of the polyacrylonitrile support for 10 minutes.

[0061] Step 3) step 2 film is taken out from baking oven, excess liquid is poured out, a large amount of room temperature ethanol is poured into membrane assembly rapidly, left standstill 40min, termination reaction. Pour out ethanol, film is taken out from assembly, left standstill in fume hood and is dried to film surface solution evaporation complete. The film obtained now is the amide-imide double network polymer film of the crystalline state and amorphous coexistence of the polyacrylonitrile support.

[0062] The permeability and selectivity of the polyacrylonitrile-supported crystalline and amorphous coexisting amide-imide dual network polymer membrane were tested at 150°C and different transmembrane pressure differences (the pressure in this patent refers to the transmembrane pressure difference): 1 bar, P H2 =64.3GPU,P CO2=6.93GPU,P H2 / P CO2 =9.28.

[0063] Example 6

[0064] Step 1) Weigh 0.3g of m-phenylenediamine at room temperature into a weighing bottle, add 19.7g of deionized water, and sonicate to fully dissolve it to obtain a 1.5wt% m-phenylenediamine aqueous solution, which is then stored in a 5°C refrigerator for 30 minutes. A polyacrylonitrile support is secured to the membrane assembly and stored in a 5°C refrigerator for 30 minutes. The prepared m-phenylenediamine aqueous solution is then slowly poured into the membrane assembly to completely submerge the polyacrylonitrile support. After 60 minutes of undisturbed standing, the excess solution is discarded and the membrane is air-dried until no visible droplets remain on the surface.

[0065] Step 2) Weigh 0.02g of 1,3,5-benzenetricarboxylic acid chloride and 0.08g of 1,3,5-benzenetricarboxaldehyde into a weighing bottle, add 19.9g of benzene, sonicate to completely dissolve, and store in a refrigerator at 5°C for 30 minutes. Slowly pour the benzene solution into the membrane assembly. The 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the solution polymerize with the m-phenylenediamine on the surface of the polyacrylonitrile support for 30 minutes.

[0066] Step 3) step 2 film is taken out from refrigerator, excess liquid is poured out, a large amount of room temperature ethanol is poured into membrane assembly rapidly, leaves standstill 60min, termination reaction. Pour out ethanol, film is taken out from assembly, leaves standstill in fume hood and is dried to film surface solution evaporation complete.The film obtained now is the crystalline state of polyacrylonitrile support and the amide-imide double network polymer film of amorphous coexistence.

[0067] The permeability and selectivity of the polyacrylonitrile-supported crystalline and amorphous coexisting amide-imide dual network polymer membrane were tested at 150°C and different transmembrane pressure differences (the pressure in this patent refers to the transmembrane pressure difference): 0 bar, P H2 =96.3GPU,P CO2 =2.82GPU,P H2 / P CO2 =34.1.

[0068] Example 7

[0069] Step 1) Weigh 0.3g of m-phenylenediamine at room temperature into a weighing bottle, add 19.7g of deionized water, and sonicate to fully dissolve it to obtain a 1.5wt% m-phenylenediamine aqueous solution, which is then stored in a 5°C refrigerator for 30 minutes. A polyacrylonitrile support is secured to the membrane assembly and stored in a 5°C refrigerator for 30 minutes. The prepared m-phenylenediamine aqueous solution is then slowly poured into the membrane assembly to completely submerge the polyacrylonitrile support. After 60 minutes of undisturbed standing, the excess solution is discarded and the membrane is air-dried until no visible droplets remain on the surface.

[0070] Step 2) Weigh 0.025g of 1,3,5-benzenetricarboxylic acid chloride and 0.075g of 1,3,5-benzenetricarboxaldehyde into a weighing bottle, add 100g of benzene, sonicate to completely dissolve, and store in a refrigerator at 5°C for 30 minutes. Slowly pour the benzene solution into the membrane assembly. The 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the solution polymerize with the m-phenylenediamine on the surface of the polyacrylonitrile support for 60 minutes.

[0071] Step 3) step 2 film is taken out from refrigerator, excess liquid is poured out, a large amount of room temperature ethanol is poured into membrane assembly rapidly, leaves standstill 60min, termination reaction. Pour out ethanol, film is taken out from assembly, leaves standstill in fume hood and is dried to film surface solution evaporation complete.The film obtained now is the crystalline state of polyacrylonitrile support and the amide-imide double network polymer film of amorphous coexistence.

[0072] The permeability and selectivity of the polyacrylonitrile-supported crystalline and amorphous coexisting amide-imide dual network polymer membrane were tested at 150°C and different transmembrane pressure differences (the pressure in this patent refers to the transmembrane pressure difference): 1 bar, P H2 =314GPU,P CO2 =45.9GPU,P H2 / P CO2 =6.90.

[0073] Example 8

[0074] Step 1) 0.3 g of m-phenylenediamine was weighed at room temperature and placed in a weighing bottle. 19.7 g of deionized water was added and thoroughly dissolved by sonication to obtain a 1.5 wt% m-phenylenediamine aqueous solution, which was then stored at 25°C for 30 minutes. A polyacrylonitrile support was secured to the membrane assembly and stored at 25°C for 30 minutes. The prepared m-phenylenediamine aqueous solution was then slowly poured into the membrane assembly to completely submerge the polyacrylonitrile support. After 60 minutes of undisturbed standing, the excess solution was discarded and the membrane was allowed to dry until no visible droplets remained on the surface.

[0075] Step 2) Weigh 0.02g of 1,3,5-benzenetricarboxylic acid chloride and 0.08g of 1,3,5-benzenetricarboxaldehyde into a weighing bottle, add 19.9g of benzene, sonicate to completely dissolve, and store at 25°C for 30 minutes. Slowly pour the benzene solution into the membrane assembly. The 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the solution polymerize with the m-phenylenediamine on the surface of the polyacrylonitrile support for 30 minutes.

[0076] Step 3) Take out the membrane prepared in step 2, pour out the excess liquid, and quickly pour a large amount of room temperature ethanol into the membrane assembly. Let it stand for 5 minutes to terminate the reaction. Pour out the ethanol, take the membrane out of the assembly, and let it stand in a fume hood to dry until the solution on the membrane surface evaporates completely. The membrane obtained at this time is an amide-imide double network polymer membrane with coexistence of crystalline and amorphous states supported by a polyacrylonitrile support. The membrane has a stability of separating H2 / CO2 mixed gas at 150°C and a transmembrane pressure difference of 5 bar. Figure 3 shown.

[0077] The permeation performance and selectivity of H2 / CO2 mixed gas of crystalline and amorphous coexisting amide-imide double network polymer membrane supported by polyacrylonitrile were tested at 150℃ and transmembrane pressure difference of 5 bar: 5 bar, P H2 =60.8GPU,P CO2 =0.994GPU,P H2 / P CO2 = 61.3. The porous organic polymer membrane supported by the organic support achieves strong pressure resistance under high temperature conditions (greater than 100°C).

[0078] Example 9

[0079] Step 1) 0.3 g of m-phenylenediamine was weighed and placed in a weighing bottle at room temperature. 19.7 g of deionized water was added and thoroughly dissolved by sonication to obtain a 1.5 wt% m-phenylenediamine aqueous solution, which was then stored in a 5°C refrigerator for 30 minutes. A γ-Al2O3 support was placed in a weighing bottle and stored in a 5°C refrigerator for 30 minutes. The prepared m-phenylenediamine aqueous solution was then slowly poured along the bottle wall to completely immerse the support. After 60 minutes of undisturbed standing, the γ-Al2O3 support was removed and air-dried until no visible droplets remained on the surface.

[0080] Step 2) Weigh 0.05g of 1,3,5-benzenetricarboxylic acid chloride and 0.05g of 1,3,5-benzenetricarboxaldehyde into a weighing bottle, add 19.9g of benzene, sonicate to completely dissolve, and store in a 5°C refrigerator for 30 minutes. Place the γ-Al2O3 support soaked in the aqueous solution in a clean glass Petri dish and store in a 5°C refrigerator for 30 minutes. Slowly pour the benzene solution into the weighing bottle to submerge the support. The 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the solution polymerize with the m-phenylenediamine on the surface of the γ-Al2O3 support for 10 minutes.

[0081] Step 3) The membrane prepared in step 2 is removed from the refrigerator and quickly placed in a large amount of room temperature ethanol. The reaction is terminated by standing for 60 minutes. The ethanol is poured out, and the membrane is allowed to dry in a fume hood until the solution on the membrane surface evaporates completely. The resulting membrane is an amide-imide dual network polymer membrane containing both crystalline and amorphous structures supported by a γ-Al2O3 support.

[0082] The H2 / CO2 mixed gas permeation performance and selectivity of the amide-imide dual network polymer membrane supported by the γ-Al2O3 support with coexistence of crystalline and amorphous phases are tested (the pressure in this patent refers to the transmembrane pressure difference): 25℃, 0 bar, P H2 =809GPU,P CO2 =41.8GPU,P H2 / P CO2 =19.3. 150℃, 0bar, P H2 =997GPU,P CO2 =48.8GPU,P H2 / P CO2 =20.4. 150℃, 1bar, P H2 =268GPU,P CO2 =11.8GPU,P H2 / P CO2 =22.7.

[0083] Example 10

[0084] Step 1) 0.3 g of m-phenylenediamine was weighed and placed in a weighing bottle at room temperature. 19.7 g of deionized water was added and thoroughly dissolved by ultrasonication to obtain a 1.5 wt% m-phenylenediamine aqueous solution, which was then stored at 25°C for 30 minutes. A γ-Al2O3 support was placed in a weighing bottle and stored at 25°C for 30 minutes. The prepared m-phenylenediamine aqueous solution was then slowly poured along the bottle wall to completely immerse the support. After standing for 30 minutes, the γ-Al2O3 support was removed and air-dried until no visible droplets remained on the surface.

[0085] Step 2) Weigh 0.04g of 1,3,5-benzenetricarboxylic acid chloride and 0.06g of 1,3,5-benzenetricarboxaldehyde separately into a weighing bottle, add 19.9g of benzene, sonicate to completely dissolve, and store at 25°C for 30 minutes. Place the γ-Al2O3 support soaked in the aqueous solution in a clean glass Petri dish and store at 25°C for 30 minutes. Slowly pour the benzene solution into the weighing bottle to submerge the support. The 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the solution polymerize with the m-phenylenediamine on the surface of the γ-Al2O3 support for 30 minutes.

[0086] Step 3) The membrane prepared in step 2 was removed and quickly placed in 20 mL of ethanol. The reaction was allowed to stand for 20 minutes to terminate the reaction. The ethanol was poured out, and the membrane was allowed to dry in a fume hood until the solution on the membrane surface evaporated completely. The resulting membrane was an amide-imide dual network polymer membrane containing both crystalline and amorphous structures supported on a γ-Al2O3 support.

[0087] The permeation performance and selectivity of H2 / CO2 mixed gas of γ-Al2O3 support-supported crystalline and amorphous coexisting amide-imide dual network polymer membrane were tested at 1 bar (the pressure in this patent refers to the transmembrane pressure difference) and different temperatures (150-250℃): 150℃, P H2 =193GPU,P CO2 =7.97GPU,P H2 / P CO2 =24.2.200℃,P H2 =288GPU,P CO2 =7.07GPU,P H2 / P CO2 =40.7.250℃, P H2 =400GPU,P CO2 =11.9GPU,P H2 / P CO2 =36.6. The film can withstand high temperatures of 250°C.

[0088] Example 11

[0089] Step 1) 0.3 g of m-phenylenediamine was weighed and placed in a weighing bottle at room temperature. 19.7 g of deionized water was added and thoroughly dissolved by sonication to obtain a 1.5 wt% m-phenylenediamine aqueous solution, which was then stored at 50°C for 30 minutes. A γ-Al2O3 support was placed in a weighing bottle and stored at 50°C for 30 minutes. The prepared m-phenylenediamine aqueous solution was then slowly poured along the bottle wall to completely immerse the support. After 30 minutes of stagnant water, the γ-Al2O3 support was removed and air-dried until no visible droplets remained on the surface.

[0090] Step 2) Weigh 0.06g of 1,3,5-benzenetricarboxylic acid chloride and 0.04g of 1,3,5-benzenetricarboxaldehyde separately into a weighing bottle, add 19.9g of benzene, sonicate to completely dissolve, and store at 50°C for 30 minutes. Place the γ-Al2O3 support soaked in the aqueous solution in a clean glass Petri dish and store at 50°C for 30 minutes. Slowly pour the benzene solution into the weighing bottle to submerge the support. The 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the solution polymerize with the m-phenylenediamine on the surface of the γ-Al2O3 support for 60 minutes.

[0091] Step 3) The membrane prepared in step 2 is removed from the oven and quickly placed in a large amount of room temperature ethanol. The reaction is terminated by allowing the membrane to stand for 20 minutes. The ethanol is then poured out, and the membrane is allowed to dry in a fume hood until the surface solution evaporates completely. The resulting membrane is an amide-imide dual-network polymer membrane containing both crystalline and amorphous structures supported by a γ-Al2O3 support.

[0092] The permeation performance and selectivity of H2 / CO2 mixed gas of γ-Al2O3 support-supported crystalline and amorphous coexisting amide-imide dual network polymer membrane were tested at 250℃ and transmembrane pressure difference of 1 bar: 1 bar, P H2 =84.6GPU,P CO2 =4.88GPU,P H2 / P CO2 =17.1.

[0093] Example 12

[0094] Step 1) 0.3 g of m-phenylenediamine was weighed and placed in a weighing bottle at room temperature. 19.7 g of deionized water was added and thoroughly dissolved by sonication to obtain a 1.5 wt% m-phenylenediamine aqueous solution, which was then stored at 80°C for 30 minutes. A γ-Al2O3 support was placed in a weighing bottle and stored at 80°C for 30 minutes. The prepared m-phenylenediamine aqueous solution was then slowly poured along the bottle wall to completely immerse the support. After 30 minutes of stagnant water, the γ-Al2O3 support was removed and air-dried until no visible droplets remained on the surface.

[0095] Step 2) Weigh 0.08g of 1,3,5-benzenetricarboxylic acid chloride and 0.02g of 1,3,5-benzenetricarboxaldehyde separately into a weighing bottle, add 19.9g of benzene, sonicate to completely dissolve, and store at 80°C for 30 minutes. Place the γ-Al2O3 support soaked in the aqueous solution in a clean glass Petri dish and store at 80°C for 30 minutes. Slowly pour the benzene solution into the weighing bottle to submerge the support. The 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the solution polymerize with the m-phenylenediamine on the surface of the γ-Al2O3 support for 10 minutes.

[0096] Step 3) The membrane prepared in step 2 is removed from the oven and quickly placed in a large amount of room temperature ethanol. The reaction is terminated by allowing the membrane to stand for 20 minutes. The ethanol is then poured out, and the membrane is allowed to dry in a fume hood until the surface solution evaporates completely. The resulting membrane is an amide-imide dual-network polymer membrane containing both crystalline and amorphous structures supported by a γ-Al2O3 support.

[0097] The permeation performance and selectivity of H2 / CO2 mixed gas of γ-Al2O3 support-supported crystalline and amorphous coexisting amide-imide dual network polymer membrane were tested at 250℃ and different transmembrane pressure differences (1-9 bar): 1 bar, P H2 =117GPU,P CO2 =5.20GPU,P H2 / P CO2 =25.2.3bar, P H2 =84.3GPU,P CO2 =1.29GPU,P H2 / P CO2 =65.3.5bar, P H2 =76.9GPU,P CO2 =0.95GPU,P H2 / P CO2 =81.0.7 bar, P H2 =69.4GPU,P CO2 =0.80GPU,P H2 / P CO2 =87.2.9bar, P H2 =65.1GPU,P CO2 =0.77GPU,P H2 / P CO2 =84.2. The membrane can withstand a transmembrane pressure differential of 9 bar under high temperature conditions, demonstrating excellent tolerance while achieving efficient H2 / CO2 separation with a selectivity exceeding 80.

[0098] Example 13

[0099] Step 1) 0.3 g of m-phenylenediamine was weighed and placed in a weighing bottle at room temperature. 19.7 g of deionized water was added and thoroughly dissolved by ultrasonication to obtain a 1.5 wt% m-phenylenediamine aqueous solution, which was then stored at 100°C for 30 minutes. A γ-Al2O3 support was placed in a weighing bottle and stored at 100°C for 30 minutes. The prepared m-phenylenediamine aqueous solution was then slowly poured along the bottle wall to completely immerse the support. After 30 minutes of stagnant water, the γ-Al2O3 support was removed and air-dried until no visible droplets remained on the surface.

[0100] Step 2) Weigh 0.02g of 1,3,5-benzenetricarboxylic acid chloride and 0.08g of 1,3,5-benzenetricarboxaldehyde separately into a weighing bottle, add 19.9g of benzene, sonicate to completely dissolve, and store at 100°C for 30 minutes. Place the γ-Al2O3 support soaked in the aqueous solution in a clean glass Petri dish and store at 100°C for 30 minutes. Slowly pour the benzene solution into the weighing bottle to submerge the support. The 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the solution polymerize with the m-phenylenediamine on the surface of the γ-Al2O3 support for 40 minutes.

[0101] Step 3) The membrane prepared in step 2 is removed from the oven and quickly placed in a large amount of room temperature ethanol. The reaction is terminated by allowing the membrane to stand for 30 minutes. The ethanol is then poured out, and the membrane is allowed to dry in a fume hood until the surface solution evaporates completely. The resulting membrane is an amide-imide dual-network polymer membrane containing both crystalline and amorphous structures supported by a γ-Al2O3 support.

[0102] The permeation performance and selectivity of H2 / CO2 mixed gas of crystalline and amorphous coexisting amide-imide double network polymer membrane supported by γ-Al2O3 support were tested at different temperatures (200-250℃) and different transmembrane pressure differences (1-6bar): 200℃, 1bar, P H2 =38.6GPU,P CO2 =0.594GPU,P H2 / P CO2 =84.5. 200℃, 2bar, P H2 =31.8GPU,P CO2 =0.465GPU,P H2 / P CO2 =87.200℃、3bar,P H2 =31.8GPU,P CO2 =0.563GPU,P H2 / P CO2 =57.7. 200℃、6bar,P H2 =24.6GPU,P CO2 =0.722GPU,P H2 / P CO2 =38.5. 250℃, 1bar, P H2 =54.8GPU,P CO2 =11.03GPU,P H2 / P CO2 =54.7.

[0103] Example 14

[0104] Step 1) 0.3 g of m-phenylenediamine was weighed and placed in a weighing bottle at room temperature. 19.7 g of deionized water was added and thoroughly dissolved by sonication to obtain a 1.5 wt% m-phenylenediamine aqueous solution, which was then stored at 80°C for 30 minutes. A γ-Al2O3 support was placed in a weighing bottle and stored at 80°C for 30 minutes. The prepared m-phenylenediamine aqueous solution was then slowly poured along the bottle wall to completely immerse the support. After 30 minutes of stagnant water, the γ-Al2O3 support was removed and air-dried until no visible droplets remained on the surface.

[0105] Step 2) Weigh 0.05g of 1,3,5-benzenetricarboxylic acid chloride and 0.05g of 1,3,5-benzenetricarboxaldehyde respectively into a weighing bottle, add 19.9g of benzene, sonicate to completely dissolve, and store at 80°C for 30 minutes. Place the γ-Al2O3 support soaked in the aqueous solution in a clean glass Petri dish and store at 80°C for 30 minutes. Slowly pour the benzene solution into the weighing bottle to submerge the support. The 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the solution polymerize with the m-phenylenediamine on the surface of the γ-Al2O3 support for 1 minute.

[0106] Step 3) Take the membrane prepared in step 2 out of the oven and quickly place it in a large amount of room temperature ethanol. Let it stand for 20 minutes to terminate the reaction. Pour out the ethanol and let the membrane stand in a fume hood to dry until the solution on the membrane surface evaporates completely. The membrane obtained at this time is an amide-imide double network polymer membrane with crystalline and amorphous coexistence supported by the γ-Al2O3 support. 13 C NMR spectroscopy confirmed that the chemical structure of the resulting polymer film contained an amide network and an imine network, such as Figure 4 As shown; transmission electron microscopy images confirm that the generated polymer film clearly shows the presence of both amorphous and crystalline regions, as shown in Figure 5 As shown in the figure, under the condition of constant temperature of 250℃ and cyclic pressure change (1-11 bar) (the pressure in this patent refers to the transmembrane pressure difference), the permeation performance and selectivity of H2 / CO2 mixed gas are as follows: Figure 6 As shown in the figure, the performance of the membrane exceeds that of most reported polymer membranes for H2 / CO2 mixed gas separation, especially the H2 / CO2 mixed gas separation performance under high temperature and high pressure conditions. Figure 7 shown.

[0107] The permeation performance and selectivity of H2 / CO2 mixed gas of γ-Al2O3 support-supported crystalline and amorphous coexisting amide-imide dual network polymer membrane at different temperatures (150-250℃) and different transmembrane pressure differences (1-11bar) are as follows: 150℃, 1bar, P H2 =207GPU,P CO2 =2.79GPU,P H2 / P CO2 =74.2。150℃、3bar,P H2 =178GPU,P CO2 =2.51GPU,P H2 / P CO2 =70.9。150℃、5bar,P H2 =168GPU,P CO2 =2.57GPU,P H2 / P CO2 =65.4。150℃、7bar,P H2 =179GPU,P CO2 =1.83GPU,P H2 / P CO2 =97.4。150℃、9bar,P H2 =159GPU,P CO2 =1.87GPU,P H2 / P CO2 =85.1。150℃、11bar,P H2 =129GPU,P CO2 =1.43GPU,P H2 / P CO2 =90.1。250℃、1bar,P H2 =405GPU,P CO2 =3.58GPU,P H2 / P CO2 =113.2。250℃、3bar,P H2 =245GPU,P CO2 =2.54GPU,P H2 / P CO2 =96.6。250℃、5bar,P H2 =203GPU,P CO2 =1.65GPU,P H2 / P CO2 =123。250℃、7bar,P H2 =211GPU,P CO2 =2.04GPU,P H2 / P CO2 =103。250℃、9bar,P H2 =238GPU,P CO2 =3.31GPU,P H2 / P CO2 =71.5。250℃、11bar,P H2 =193GPU,P CO2 =3.24GPU,P H2 / PCO2 =59.4. The membrane exhibits exceptional tolerance and maintains excellent H2 permeability and H2 / CO2 selectivity under continuous and multiple changes in operating temperature and pressure.

[0108] The permeation performance and selectivity of the mixed gas of H2 / CO2 / H2O (water vapor) of the amide-imide dual network polymer membrane with coexistence of crystalline and amorphous amides supported by the γ-Al2O3 support were tested at 150℃ and 1 bar transmembrane pressure difference: P H2 =162GPU,P CO2 =1.8GPU,P H2 / P CO2 = 90. The membrane has water vapor tolerance under high temperature conditions and has the potential for effective H2 / CO2 separation under actual industrial conditions.

[0109] The above embodiment embodies the present invention's dual-network polymer membrane with coexisting crystalline and amorphous states and its preparation method. In a constant temperature and humidity environment, a support is immersed in an aqueous solution of m-phenylenediamine, removed, and allowed to stand until no visible droplets remain on the support surface. The support is then immersed in an organic solution of 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde, where a polymerization reaction occurs on the support surface to produce a dual-network polymer membrane. The present invention utilizes an interfacial polymerization strategy in a constant temperature and humidity environment to prepare a continuous, defect-free, and intergrown dual-network polymer membrane with coexisting crystalline and amorphous states. The prepared polymer membrane exhibits excellent H2 / CO2 separation performance in a high-temperature and high-pressure system. At 150°C and a transmembrane pressure difference of 1 bar, the H2 permeability is 207 GPU and the H2 / CO2 selectivity is 76. At 150°C and a transmembrane pressure difference of 11 bar, the H2 permeability is 128 GPU and the H2 / CO2 selectivity is 90. Even when water vapor is present in the feed gas, the H2 permeability can reach 162 GPU and the H2 / CO2 selectivity can reach 90. The method of the present invention is simple to operate and has a short preparation cycle. It has high gas permeability, high selectivity, good stability, and is easy to prepare on a large scale under high temperature and high pressure, and has potential for practical industrial application.

[0110] The present invention discloses and proposes a crystalline and amorphous coexisting amide-imide dual-network polymer membrane and its preparation method and application. Those skilled in the art can achieve this by referring to the contents of this article and appropriately changing the conditions and routes. Although the methods and preparation techniques of the present invention have been described through preferred embodiments, relevant technicians can obviously modify or recombine the methods and technical routes described herein without departing from the content, spirit, and scope of the present invention to achieve the final preparation technology. It is particularly important to point out that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in the spirit, scope, and content of the present invention.

Claims

1. A crystalline and amorphous coexisting amide-imide double network polymer film; characterized in that: In the matrix of the amide-imide linked amorphous polymer film, there exists a crystalline polymer structure with the same or similar molecular structure.

2. The method for preparing a crystalline and amorphous coexisting amide-imide double network polymer film according to claim 1, characterized in that: The steps include: 1) Soaking the support in an aqueous solution of m-phenylenediamine at the reaction temperature for 10 to 60 minutes, allowing the solution to fully penetrate the support, then removing the solution and allowing it to stand until no obvious droplets remain on the surface of the support; 2) The support obtained in the first step is immersed in an organic solution of 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde preheated to the reaction temperature of step 1), and the m-phenylenediamine in the support reacts with 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde on the surface of the support to form an amide-imide double network polymer membrane, and the reaction time is 1 to 60 minutes; 3) The amide-imide double network polymer membrane prepared in the second step is placed in room temperature ethanol, allowed to stand for 5 to 60 minutes to terminate the reaction, taken out, and naturally dried in a fume hood; an amide-imide double network polymer membrane in which crystalline and amorphous states coexist is obtained.

3. The method for preparing the amide-imide double network polymer film in which crystalline and amorphous coexist as claimed in claim 2, wherein: In the step 1), the support body comprises one of an Al2O3 ceramic sheet, a ceramic tube, polysulfone, polyacrylonitrile, polyimide or a stainless steel support body.

4. The method for preparing the amide-imide double network polymer film in which crystalline and amorphous coexist as claimed in claim 2, wherein: The mass percentage concentration of m-phenylenediamine in the aqueous solution of m-phenylenediamine in step 1) is 0.01 to 15 wt %, preferably 0.15 to 1.5 wt %.

5. The method for preparing the amide-imide double network polymer film in which crystalline and amorphous coexist as claimed in claim 2, wherein: In the step 1), the support is immersed in the m-phenylenediamine aqueous solution and allowed to stand for 10 to 20 minutes.

6. The method for preparing the amide-imide double network polymer film in which crystalline and amorphous coexist as claimed in claim 2, wherein: The organic solvent in step 2) includes benzene or toluene, and the reaction temperature is 5 to 100°C, preferably 60 to 80°C.

7. The method for preparing the amide-imide double network polymer film in which crystalline and amorphous coexist as claimed in claim 2, wherein: In the step 2), the mass percentage concentration of the solute in the organic solution containing 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde is 0.01 to 1 wt %, preferably 0.1 to 0.5 wt %.

8. The method for preparing the amide-imide double network polymer film in which crystalline and amorphous coexist as claimed in claim 2, wherein: In the step 2), the mass ratio of 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde in the organic solution containing 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxylic acid chloride is 20-80%, preferably 50%.

9. The method for preparing the amide-imide double network polymer film in which crystalline and amorphous coexist as claimed in claim 1, wherein: In the step 2), the interfacial polymerization of the m-phenylenediamine aqueous solution and the 1,3,5-benzenetricarboxylic acid chloride and 1,3,5-benzenetricarboxaldehyde organic solution on the support surface is carried out for 1 to 10 minutes to obtain an amide-imide double network polymer film in which crystalline and amorphous coexist.

10. The amide-imide double network polymer membrane of claim 1 in which crystalline and amorphous coexist, is used in a H2 / CO2 system; the separation temperature range is 25 to 250°C, and the transmembrane pressure difference is 1 to 11 bar.

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