Composite resin and preparation method and application thereof, gas separation membrane and preparation method and application thereof

Abstract

The invention relates to the field of high polymer materials, in particular to composite resin and a preparation method and application thereof, and a gas separation membrane and a preparation method and application thereof. The composite resin comprises polyimide and a zeolite molecular sieve chemically bonded with amino groups on the surface. The polyimide composite resin provided by the invention is high in gas permeability coefficient and difficult to plasticize, and relieves the Trade-off effect to a certain extent. The method is especially suitable for preparation of gas separation membranes.

Description

Technical Field

[0001] This invention relates to the field of polymer materials, specifically to a composite resin and its preparation method and application, and a gas separation membrane and its preparation method and application. Background Technology

[0002] Polyimide is a high-performance polymer composed of linear molecular backbones containing imide rings, with a molecular chain spacing of 0.3-0.5 nm. Based on its membrane material characteristics, it can be applied to the field of gas separation membranes: (1) High thermal stability and high glass transition temperature (Tg), suitable for gas separation at certain high temperatures, while maintaining high permeability and high selectivity; (2) Good film-forming properties and high mechanical properties, making it easy to manufacture membrane modules, enabling the membrane modules to withstand high working pressures; (3) Good chemical resistance and high tolerance to acidic gases, which can prevent impurity gases from damaging the membrane structure and affecting the membrane separation effect; (4) Molecular chains are easy to control and have diverse structures, allowing for the design and synthesis of membrane materials with different molecular chains for different separation targets, while also possessing high permeability and high selectivity. In the 1980s, Ube Industries, Inc. of Japan first developed a biphenyl-type polyimide hollow fiber gas membrane separator for separating H2 / N2 and H2 / CH4.

[0003] The separation and purification of gas mixtures are essential steps for gas products to meet application requirements. Various gas separation methods exist, such as cryogenic separation, pressure swing adsorption (PSA), membrane separation, permeation separation, and chemical reaction separation. Among these, membrane separation eliminates the need for additional energy transfer required by cryogenic separation (refrigeration), PSA (gas pressurization), and chemical reaction separation (consuming additional raw materials), resulting in low energy consumption and simple processes, thus earning it the title of "green technology." In 1979, Monsanto in the United States developed a hollow fiber N2 / H2 separation membrane and successfully applied it to recover hydrogen from synthetic ammonia waste gas. Since then, gas separation membranes have seen significant development. Currently, gas separation membranes demonstrate enormous application potential in hydrogen recovery, natural gas purification, carbon dioxide capture, and gas separation.

[0004] Currently used gas separation membranes are mainly classified into the following types: (1) Inorganic porous membranes. These are divided into macroporous membranes, mesoporous membranes, and microporous membranes, including zeolite membranes, carbon molecular sieve membranes, and metal-organic framework (MOF) membranes. During the separation process, the difference between the dynamic diameter of the gas and the membrane pore size determines the transport mode of the gas in the membrane: when the membrane pore size is smaller than the mean free path of the gas, the gas molecules follow Knudsen diffusion in the membrane, and the smaller the molecular mass, the faster the diffusion rate; when gas molecules are adsorbed on the pore wall surface, the gas molecules will diffuse along the surface through the membrane, and the concentration gradient and the binding strength with the surface determine the diffusion rate and separation effect; when condensable gases are adsorbed on the pore wall surface and fill the pores, they will restrict the passage of non-condensable gases, resulting in capillary condensation; when the membrane pore size is between the diameters of the two gas components to be separated, the smaller diameter gas can pass through the membrane pores, while the larger diameter gas is blocked, achieving molecular sieving. (2) Organic polymer membranes. It is divided into glassy polymer membranes and rubbery polymer membranes, using polymer materials such as cellulose acetate (CA), polysulfone (PSF) and polyimide (PI). Organic polymer membranes separate gas mixtures through a dissolution-diffusion-desorption mechanism. Gases that are easily soluble in the organic matrix are preferentially adsorbed on the membrane surface, and then diffuse within the membrane under the action of the concentration gradient and desorbed on the downstream side. (3) Mixed matrix membranes (MMMs). MMMs are gas separation membranes with both separation performance and mechanical stability, made by adding inorganic materials as a dispersed phase to a polymer matrix. Inorganic materials provide gas transport channels to reduce diffusion resistance, and increase the interchain spacing of the polymer matrix to enhance solubility and diffusivity, so that gas transfer changes from a single dissolution-diffusion-desorption mechanism to the combined action of multiple transport mechanisms. The interface morphology between inorganic materials and polymers seriously affects the gas separation process. When there is a large difference in affinity between inorganic materials and organic phases, MMMs will have problems such as "interfacial voids", "molecular chain rigidity" and "pore blockage". (4) Multilayer composite membranes. An ultrathin organic selective layer is coated onto a porous support membrane with good mechanical strength. The support membrane provides mechanical strength without affecting the gas molecule permeation process, while reducing the thickness of the organic selective layer enables rapid gas molecule permeation without affecting the selectivity of gas separation. The porous support membrane can be polyacrylonitrile (PAN), polysulfone (PSF), or alumina. To prevent the organic selective layer from permeating into the pore structure of the support membrane and forming a permeable layer, a high-permeability intermediate layer, such as a siloxane membrane layer, can be pre-coated between the porous support membrane and the organic selective layer.

[0005] The application of polyimide (PI) in gas separation membranes still faces challenges such as low gas permeability, easy plasticization, and the trade-off effect. The high molecular chain packing density and strong interactions in PI membranes significantly reduce the gas permeability. Under high pressure, the induced plasticization of PI membrane molecular chains by gases such as CO2 rapidly decreases the selectivity / separation factor of the mixed gas. Like other types of gas separation membranes, PI membranes also exhibit a trade-off between permeability and selectivity, known as the "Robertson upper bound" or trade-off effect. These problems severely hinder the widespread industrial application of PI membranes.

[0006] Permeability coefficient and separation factor are the main parameters for evaluating the separation performance of organic membranes. The permeability coefficient (P) is the product of the solubility coefficient (S) and the diffusion coefficient (D): P = S × D. The solubility coefficient S mainly depends on the condensability of the gas and the affinity between gas molecules and the membrane matrix; the diffusion coefficient D depends on the free volume of the polymer in the membrane material. The separation factor (α) is the ratio of the membrane's permeability coefficient to that of the mixed gas: α = P A / P B =(S A / S B )×(D A / D B Currently, researchers have proposed many improvement plans, and the improvement effects are significant.

[0007] Researchers have improved gas permeability by manipulating the chemical structure of polyimide molecular chains. Introducing flexible groups such as ether bonds, isopropyl groups, and ketone groups into the main chain enhances chain mobility and increases the gas diffusion coefficient. Introducing substituents such as methyl, polyaromatic, naphthyl, and binaphthyl groups into the side chains reduces packing density, increases free volume, and improves the gas diffusion coefficient. Introducing functional groups such as trifluoromethyl and sulfonic acid groups into the molecular chain not only increases interchain free volume but also enhances the number and strength of hydrogen bond sites, thereby increasing the solubility coefficient of gases such as CO2 and improving gas permeability. However, the increased gas permeability leads to a decrease in the separation factor and a severe trade-off effect; the plasticization of CO2 under high pressure cannot be avoided either.

[0008] Researchers have blended polymers with high resistance to plasticization with polyimide to improve the solubility of gases such as CO2. For example, blending sulfuric acid-sulfonated polyether ether ketone (SPEEK) with soluble polyimide Matrimid enhances the water absorption and swelling capacity of the blended membrane, promoting the diffusion and transport of gases such as CO2 within the membrane and improving the separation factor. The membrane's resistance to plasticization is also enhanced. However, if the polymers have poor miscibility, a sponge-like structure can appear within the membrane, limiting the improvement of the blended membrane's gas separation performance. Poor miscibility with polyimide limits the use of most polymers.

[0009] Researchers have introduced cross-linking-capable covalent or ionic bonds into the polymer backbone, attempting to suppress CO2-induced plasticization through cross-linking modification. Yan Jie et al. thermally oxidatively cross-linked PI membranes, improving the CO2 gas permeability coefficient and CO2 / CH4 separation factor, and also enhancing resistance to CO2 and other gases. Hossain et al. cross-linked PEG with different chain lengths and ionic groups containing diimidazole with polyimide; the cross-linking process effectively prevented CO2-induced plasticization of the PI membrane; the ionic groups used also improved CO2 selectivity. However, regardless of whether it's thermal cross-linking, chemical modification, UV irradiation, or ion beam irradiation, the harsh atmosphere and conditions can accelerate PI membrane aging, causing densification or damage to the porous support layer structure in the composite separation membrane, thus reducing the membrane's mechanical strength.

[0010] Researchers also modified polyimide films by incorporating inorganic nanofillers. The filler systematically controls the stacking of molecular chains, effectively increasing the interchain spacing and thus enhancing the gas permeability coefficient. When the filler size is small and the specific surface area is large, its separation factor also shows a significant improvement. However, polyimide, as a glassy polymer with relatively rigid molecular chains, has poor compatibility with inorganic nanofillers, leading to the appearance of non-selective interfacial pores and a decrease in the membrane separation factor.

[0011] Researchers have also begun using MOF materials as modifying additives for polyimide gas separation membranes. The organic ligands in the MOF framework have strong interactions with the polyimide matrix, exhibiting high compatibility and effectively preventing the formation of interfacial cavities. The high specific surface area and porosity of MOFs also improve gas permeability. Grafting / loading specific functional groups onto the MOF surface and pores to regulate the pore structure and function of MOFs can further enhance the CO2 / CH4 gas separation factor. For example, introducing amino functional groups into MOFs improves the solubility of CO2 molecules due to the affinity between CO2 and amino functional groups, significantly increasing the CO2 / CH4 gas separation factor. Summary of the Invention

[0012] The purpose of this invention is to overcome the problems of high molecular chain packing density and strong interaction of polyimide resin in the prior art, which result in low gas permeability coefficient, easy plasticization, and trade-off effect. This invention provides a composite resin and its preparation method and application, as well as a gas separation membrane and its preparation method and application. The composite resin has a high gas permeability coefficient and is not easily plasticized, which alleviates the trade-off effect to a certain extent.

[0013] To achieve the above objectives, a first aspect of the present invention provides a composite resin comprising: a polyimide obtained by polymerization of a diamine and a dianhydride, having the following structure:

[0014]

[0015] Wherein, 500≥m+n≥20; 0.5≤m / (m+n)≤1, m and n are natural numbers, Ar is a dianhydride residue that is not 6FDA, B is a diamine residue, the diamine includes fluoroalkyl-substituted diamines, and the molar percentage of fluoroalkyl-substituted diamines in the diamine is not less than 50%; and, zeolite molecular sieves with amino groups chemically bonded to their surface.

[0016] A second aspect of the present invention provides a method for preparing the composite resin described in the first aspect, the method comprising the following steps:

[0017] (1) Preparation of polyamic acid solution, including: dispersing zeolite molecular sieve and diamine compound in solvent under inert atmosphere; adding dianhydride compound to solution to carry out polymerization reaction;

[0018] (2) Heat treatment, including: after removing part of the solvent from the polyamic acid solution, heat treatment is carried out in a nitrogen atmosphere.

[0019] The third aspect of this invention provides the application of the composite resin described in the first aspect and / or the preparation method described in the second aspect in the preparation of gas separation membranes.

[0020] A fourth aspect of the present invention provides a gas separation membrane comprising the composite resin described in the first aspect and / or the composite resin prepared by the preparation method described in the second aspect.

[0021] The fifth aspect of the present invention provides a method for preparing the gas separation membrane described in the fourth aspect, the method comprising the following steps: (1) preparation of a polyamic acid solution, comprising: dispersing zeolite molecular sieves and diamine compounds in a solvent under a nitrogen atmosphere; adding dianhydride compounds to the solution for polymerization reaction; (2) coating membrane formation, comprising: coating the polyamic acid solution of step (1) onto a carrier, desolventizing to a solvent content of 15-25 wt%, and obtaining a dry membrane; (3) heat treatment, comprising: heat treating the dry membrane under a nitrogen atmosphere.

[0022] The sixth aspect of the present invention provides an application of the gas separation membrane described in the fourth aspect in the separation of CH4 / CO2 mixed gases.

[0023] Through the above technical solution, the present invention has the following advantages:

[0024] The polyimide composite resin containing the composition of this invention has a high gas permeability coefficient and is not easily plasticized, which alleviates the trade-off effect to some extent. It is particularly suitable for the preparation of gas separation membranes.

[0025] The film product prepared from the composite resin of this invention uses trifluoromethyl-substituted polyimide as the polymer substrate. Different types of gas molecules have different solubility and diffusion coefficients within the polyimide film, and these differential solubility and diffusion coefficients enable the polyimide film to achieve selective gas separation. The trifluoromethyl functional groups present on the polyimide molecular chain increase the interchain spacing, allowing gas molecules to pass through more easily, thereby increasing the gas diffusion coefficient and improving the gas permeability. Furthermore, as a high-heat-resistant and high-mechanical-strength polymer material, polyimide, when used to make gas separation membranes, ensures that the final gas separation membrane product has excellent tensile strength and mechanical properties, enabling the gas separation membrane to be used stably for a long time at high temperatures.

[0026] The thin film product prepared from the composite resin of this invention incorporates zeolite molecular sieves with amino functional groups as a dopant to optimize gas separation performance. The zeolite molecular sieves, acting as isolated islands, are embedded within the polyimide resin film. Introducing zeolite molecular sieves into the polyimide film creates microporous channels within the otherwise poreless polymer film, resulting in a more significant improvement in gas diffusion and permeability compared to increasing the interchain spacing of polymer molecules. The continuous polymer substrate within the polyimide resin film ensures that gas molecules still permeate through a dissolution-diffusion process; therefore, the gas separation factor is not reduced due to the doping of zeolite molecular sieves. The increased gas permeability and gas separation factor enhance gas separation efficiency.

[0027] In this invention, the amino groups on the surface of the zeolite molecular sieve particles can undergo condensation polymerization with tetracarboxylic dianhydride compounds to form imide groups. Therefore, polyimide molecular chains can be chemically bonded to the particle surface, resulting in a tight bond between the zeolite molecular sieve and the polyimide resin, avoiding the formation of interfacial cavities. Inside the zeolite molecular sieve, a large number of Si-OH groups still exist on the pore surface. When the gas separation membrane of this invention is used for CO2 / CH4 gas separation, these Si-OH groups on the molecular sieve pore surface have good hydrogen bonding and affinity with CO2 molecules, improving the CO2 adsorption capacity and significantly enhancing the solubility and diffusion coefficients of CO2 molecules. Conversely, there is no hydrogen bonding between Si-OH groups and CH4 molecules. The hydrophilic Si-OH groups and the hydrophilic zeolite molecular sieve pore surface repel the hydrophobic CH4 molecules, reducing the solubility and diffusion coefficients of CH4 molecules. Therefore, the doping of the zeolite molecular sieve increases the CO2 gas permeability coefficient, decreases the CH4 gas permeability coefficient, and improves the CO2 / CH4 gas separation factor and selectivity. Detailed Implementation

[0028] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0029] This invention provides a composite resin, which comprises:

[0030] Polyimide (PI) has the following structure:

[0031]

[0032] Wherein, 500≥m+n≥20; 0.5≤m / (m+n)≤1, m and n are natural numbers, i.e., n can be 0, Ar is a dianhydride residue that is not 6FDA, B is a diamine residue, the diamine includes fluoroalkyl-substituted diamines, and the molar percentage of fluoroalkyl-substituted diamines in the diamine is not less than 50%; and,

[0033] Zeolite molecular sieves with amino groups chemically bonded to their surface.

[0034] The polyimide composite resin containing the composition of this invention has a high gas permeability coefficient and is not easily plasticized, which alleviates the trade-off effect to some extent. It is particularly suitable for the preparation of gas separation membranes.

[0035] According to a preferred embodiment of the present invention, in the structure, 300≥m+n≥20; 0.5≤m / (m+n)≤0.8.

[0036] According to a preferred embodiment of the present invention, the dianhydride comprises at least one selected from pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-terephthalodioxydiphthalic anhydride, bisphenol A type diether dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride.

[0037] According to a preferred embodiment of the present invention, the fluoroalkyl-substituted diamine is a fluoroC1-C5 alkyl group, preferably a trifluoroC1-C5 alkyl group, and more preferably a trifluoromethyl group.

[0038] According to a preferred embodiment of the present invention, the fluoroalkyl-substituted diamine includes 2,2'-bis(trifluoromethyl)diaminobiphenyl and / or 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane.

[0039] According to a preferred embodiment of the present invention, the diamine further contains other diamines, including at least one selected from p-phenylenediamine, m-phenylenediamine, benzidine, 4,4'-diaminobenzoylaniline, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodibenzophenone, 4,4'-diaminodiphenyl sulfone, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, 1,3-bis(4'-aminophenoxy)benzene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,4-cyclohexanediamine, 1,6-hexanediamine, and polyetheramine D-2000, preferably at least two.

[0040] As the number of trifluoromethyl substituents on the PI molecular chain increases, the interchain spacing of the PI molecules increases; this increased spacing promotes gas diffusion within the resin. Furthermore, the trifluoromethyl functional group has a better affinity for some gases, such as CO2, and can significantly improve the CO2 gas permeability coefficient. According to a preferred embodiment of the present invention, the molar percentage of fluoroalkyl-substituted diamines in the diamine is 60-100%.

[0041] According to a preferred embodiment of the present invention, taking Example 1 as an example, the reaction process includes:

[0042]

[0043] Surface modification of amino functional groups in zeolite molecular sieves can effectively improve the mechanical properties of resins after zeolite molecular sieve doping. It improves the tensile strength and elongation at break of the resin, while also making the bonding between the polymer and the zeolite molecular sieve tighter, effectively preventing the formation of interfacial cavities. According to a preferred embodiment of the present invention, the distribution density of amino groups on the surface of the zeolite molecular sieve is 0.001-0.02 mmol / g, preferably 0.01-0.02 mmol / g.

[0044] The pore size of zeolite molecular sieves affects gas permeation efficiency. For example, when used to separate CO2 / CH4 gases after being film-formed, as the pore size of the zeolite molecular sieve gradually increases, the CO2 gas permeability coefficient gradually increases, while the CO2 / CH4 gas separation factor slightly decreases. Increasing the pore size increases the gas permeability coefficient; simultaneously, the distance between gas molecules and the pore surface increases, slightly reducing the influence of the pore surface structure on the adsorption / repulsion of CO2 or CH4 gases, weakening the adsorption / repulsion effect of surface Si-OH groups, and thus slightly decreasing the CO2 / CH4 gas separation factor. According to a preferred embodiment of the present invention, the main channel pore size of the zeolite molecular sieve is 0.3-1.0 nm.

[0045] The particle size of zeolite molecular sieves affects gas separation efficiency. For example, when used to separate CO2 / CH4 gases after being film-formed, smaller particle sizes increase the number of particles per unit volume of resin, reducing the distance between particles. As CO2 / CH4 gas molecules permeate from one surface of the PI film to the other, they encounter more zeolite molecular sieve particle / PI resin interfaces, resulting in more separation processes for CO2 / CH4. The resin thickness permeated in a single separation process is also reduced, significantly increasing the separation efficiency. According to a preferred embodiment of the present invention, the molecular sieve particle size is 0.5-2.0 μm.

[0046] According to a preferred embodiment of the present invention, the specific surface area of ​​the zeolite molecular sieve is 400-1000 m². 2 / g.

[0047] According to a preferred embodiment of the present invention, the zeolite molecular sieve includes at least one of type A zeolite, type X zeolite, type Y zeolite, mordenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-8 zeolite, ZSM-48 zeolite, ZSM-35 zeolite, β molecular sieve, 13X molecular sieve, Silicalite-1 molecular sieve, and SSZ-23 zeolite.

[0048] The doping amount of zeolite molecular sieve affects the gas permeability coefficient and gas separation factor of the resin. For example, when it is used for CO2 / CH4 gas separation after being film-formed, the CO2 gas permeability coefficient continuously increases with the increase of zeolite molecular sieve doping in the PI film; moreover, the CO2 / CH4 gas separation factor also increases to a certain extent. This indicates that the doping of zeolite molecular sieve can increase the CO2 gas permeability coefficient while decreasing the CH4 gas permeability coefficient, thereby improving the CO2 / CH4 gas separation factor. This result is attributed to the pore structure of the zeolite molecular sieve: although the pore diameter allows CO2 and CH4 gases to pass through smoothly, the Si-OH on the pore surface promotes the adsorption and diffusion coefficient of CO2 gas and has a repulsive effect on CH4 gas, thus improving the CO2 / CH4 gas separation factor. According to a preferred embodiment of the present invention, the weight percentage of the zeolite molecular sieve in the composite resin is 0.5-5.0%, and the weight percentage of the polyimide in the composite resin is 95-99.5%.

[0049] In this invention, there are no special requirements for the preparation method of the composite resin; it is usually a conventional method in the art. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the preparation method of the composite resin includes the following steps:

[0050] (1) Preparation of polyamic acid solution, including: dispersing zeolite molecular sieve and diamine compound in solvent under inert atmosphere; adding dianhydride compound to solution to carry out polymerization reaction;

[0051] (2) Heat treatment, including: after removing part of the solvent from the polyamic acid solution, heat treatment is carried out in a nitrogen atmosphere.

[0052] In this invention, the temperature at which the zeolite molecular sieve and diamine compounds are dispersed in the solvent is typically between 5 and 45°C.

[0053] In this invention, the conditions for the polymerization reaction can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the conditions for the polymerization reaction include: a temperature of 5-45°C; and a reaction time depending on the specific reaction conditions, usually 4-48 hours.

[0054] In this invention, there are no special requirements for the feeding method of dianhydride compounds. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the dianhydride compounds are added in steps, such as in two, three, or four steps, with each addition not exceeding 60% of the total weight of the compounds. When the compounds are added in three steps, the amount added each time accounts for 50-60%, 20-30%, and 10-20% of the total weight of the dianhydride compounds, respectively, according to the feeding order.

[0055] According to a preferred embodiment of the present invention, the solid content of the polyamic acid solution is 10-25 wt%.

[0056] In this invention, there are no special requirements for the selection of solvent in step (1). The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the solvent is a strongly polar solvent, preferably at least one of N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), and m-cresol.

[0057] According to a preferred embodiment of the present invention, the temperature of the heat treatment is 280-350°C.

[0058] In this invention, there are no particular requirements for the method of amino modification of zeolite molecular sieves; it is usually a conventional method in the art. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the method for preparing the zeolite molecular sieve includes: under solvent and catalyst conditions, H... + Type zeolite molecular sieve and aminopropyltrimethoxysilane are in contact.

[0059] In this invention, the choice of catalyst is not particularly required. According to a preferred embodiment of the invention, the catalyst is concentrated hydrochloric acid and / or glacial acetic acid.

[0060] According to a preferred embodiment of the present invention, the contact conditions include: reacting at 110-120°C for 12-24 hours under reflux conditions, typically with dynamic mixing, such as stirring.

[0061] In this invention, an inert atmosphere refers to a gaseous atmosphere that does not participate in the reaction, such as a nitrogen atmosphere.

[0062] This invention provides an application of the composite resin described above and / or the composite resin prepared by the preparation method described above in the preparation of gas separation membranes.

[0063] The film product prepared from the composite resin of this invention uses trifluoromethyl-substituted polyimide as the polymer substrate. Different types of gas molecules have different solubility and diffusion coefficients within the polyimide film, and these differential solubility and diffusion coefficients enable the polyimide film to achieve selective gas separation. The trifluoromethyl functional groups present on the polyimide molecular chain increase the interchain spacing, allowing gas molecules to pass through more easily, thereby increasing the gas diffusion coefficient and improving the gas permeability. Furthermore, as a high-heat-resistant and high-mechanical-strength polymer material, polyimide, when used to make gas separation membranes, ensures that the final gas separation membrane product has excellent tensile strength and mechanical properties, enabling the gas separation membrane to be used stably for a long time at high temperatures.

[0064] The thin film product prepared from the composite resin of this invention incorporates zeolite molecular sieves with amino functional groups as a dopant to optimize gas separation performance. The zeolite molecular sieves, acting as isolated islands, are embedded within the polyimide resin film. Introducing zeolite molecular sieves into the polyimide film creates microporous channels within the otherwise poreless polymer film, resulting in a more significant improvement in gas diffusion and permeability compared to increasing the interchain spacing of polymer molecules. The continuous polymer substrate within the polyimide resin film ensures that gas molecules still permeate through a dissolution-diffusion process; therefore, the gas separation factor is not reduced due to the doping of zeolite molecular sieves. The increased gas permeability and gas separation factor enhance gas separation efficiency.

[0065] In this invention, the amino groups on the surface of the zeolite molecular sieve particles can undergo a condensation reaction with tetracarboxylic dianhydride compounds to form imide groups. Therefore, the polyimide molecular chains can be fixed to the particle surface through chemical bonds, resulting in a tight bond between the zeolite molecular sieve and the polyimide resin, thus avoiding the formation of interfacial cavities. Inside the zeolite molecular sieve, a large number of Si-OH groups still exist on the surface of the pores.

[0066] The present invention provides a gas separation membrane comprising the composite resin described above and / or the composite resin prepared by the aforementioned preparation method.

[0067] The thickness of the PI membrane significantly affects the permeability coefficient of certain gases, such as CO2. According to a preferred embodiment of the present invention, the thickness of the gas separation membrane is 10-30 μm.

[0068] This invention does not impose any particular requirements on the preparation method of the gas separation membrane; the method is usually a conventional choice in the art. The following is an illustrative description, but it does not limit the scope of the invention. The preparation method of the gas separation membrane in this invention includes the following steps:

[0069] (a) Preparation of polyamic acid solution, including: dispersing zeolite molecular sieves and diamine compounds in a solvent under a nitrogen atmosphere; adding dianhydride compounds to the solution to carry out a polymerization reaction;

[0070] (b) Coating film preparation, including: coating the polyamic acid solution of step (1) onto a carrier, desolventizing to a solvent content of 15-25 wt%, and obtaining a dry film;

[0071] (c) Heat treatment, including: heat treatment of the dry film in a nitrogen atmosphere.

[0072] The present invention provides an application of the aforementioned gas separation membrane in the separation of CH4 / CO2 mixed gases.

[0073] In this invention, the amino groups on the surface of the zeolite molecular sieve particles can undergo condensation polymerization with tetracarboxylic dianhydride compounds to form imide groups. Therefore, polyimide molecular chains can be chemically bonded to the particle surface, resulting in a tight bond between the zeolite molecular sieve and the polyimide resin, avoiding the formation of interfacial cavities. Inside the zeolite molecular sieve, a large number of Si-OH groups still exist on the pore surface. When the gas separation membrane of this invention is used for CO2 / CH4 gas separation, these Si-OH groups on the molecular sieve pore surface have good hydrogen bonding and affinity with CO2 molecules, improving the CO2 adsorption capacity and significantly enhancing the solubility and diffusion coefficients of CO2 molecules. Conversely, there is no hydrogen bonding between Si-OH groups and CH4 molecules. The hydrophilic Si-OH groups and the hydrophilic zeolite molecular sieve pore surface repel the hydrophobic CH4 molecules, reducing the solubility and diffusion coefficients of CH4 molecules. Therefore, the doping of the zeolite molecular sieve increases the CO2 gas permeability coefficient, decreases the CH4 gas permeability coefficient, and improves the CO2 / CH4 gas separation factor and selectivity.

[0074] The present invention will be described in detail below through examples. In the following examples, the pore size, specific surface area, and particle size of the zeolite molecular sieves are data obtained from the supplier; the amino content of the zeolite molecular sieves after treatment is calculated based on the amount of aminopropyltrimethoxysilane and zeolite molecular sieve used during treatment. Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0075] Preparation Example B201

[0076] The methods for modifying the amino functional groups of zeolite molecular sieves are as follows:

[0077] (1) Acid washing: Add 10g of KA type zeolite molecular sieve to 100ml of 0.1mol / L hydrochloric acid solution, and heat treat for 12h under stirring and reflux to fully remove K. + Ions; then the powder was filtered, washed, and dried to obtain H. + Type zeolite molecular sieve;

[0078] (2) Surface modification of amino functional groups: 10g H + The type zeolite molecular sieve was added to 100 ml of toluene solvent, followed by 0.02 g of aminopropyltrimethoxysilane, 150 μL of concentrated hydrochloric acid, and 350 μL of glacial acetic acid. The mixture was stirred and reacted under reflux at 110 °C for 12 h. The powder was then filtered, washed, and dried to obtain the amino-functionalized modified zeolite molecular sieve.

[0079] Preparation Example B202

[0080] The methods for modifying the amino functional groups of zeolite molecular sieves are as follows:

[0081] (1) Acid washing: Add 10g of NaA type zeolite molecular sieve to 100ml of 0.5mol / L hydrochloric acid solution, and heat treat for 8h under stirring and reflux to fully remove Na. + Ions; then the powder was filtered, washed, and dried to obtain H. + Type zeolite molecular sieve;

[0082] (2) Surface modification of amino functional groups: 10g H + The zeolite molecular sieve was added to 100 ml of toluene solvent, followed by 0.04 g of aminopropyltrimethoxysilane, 150 μL of concentrated hydrochloric acid, and 350 μL of glacial acetic acid. The mixture was stirred and reacted under reflux at 110 °C for 12 h. The powder was then filtered, washed, and dried to obtain the amino-functionalized modified zeolite molecular sieve.

[0083] Preparation Example B203

[0084] The methods for modifying the amino functional groups of zeolite molecular sieves are as follows:

[0085] (1) Acid washing: Add 10g of CaA type zeolite molecular sieve to 100ml of 1mol / L hydrochloric acid solution, and heat treat for 4h under stirring and reflux to fully remove Ca. 2+ Ions; then the powder is filtered, washed, and dried to obtain H+ type zeolite molecular sieve;

[0086] (2) Surface modification of amino functional groups: 10g of H+ type zeolite molecular sieve was added to 100ml of toluene solvent, followed by 0.004g of aminopropyltrimethoxysilane, 150uL of concentrated hydrochloric acid and 350uL of glacial acetic acid. The mixture was stirred and reacted under reflux at 110℃ for 12h. The powder was then filtered, washed and dried to obtain zeolite molecular sieve modified with amino functional groups.

[0087] Preparation Example B204

[0088] The methods for modifying the amino functional groups of zeolite molecular sieves are as follows:

[0089] (1) Acid washing: 10g of X-type zeolite molecular sieve was added to 100ml of 1mol / L hydrochloric acid solution and heat-treated for 6h under stirring and reflux to remove metal cations; then the powder was filtered, washed and dried to obtain H+ type zeolite molecular sieve.

[0090] (2) Surface modification of amino functional groups: 10g of H+ type zeolite molecular sieve was added to 100ml of toluene solvent, followed by 0.08g of aminopropyltrimethoxysilane, 150uL of concentrated hydrochloric acid and 350uL of glacial acetic acid. The mixture was stirred and reacted under reflux at 110℃ for 12h. The powder was then filtered, washed and dried to obtain zeolite molecular sieve modified with amino functional groups.

[0091] Preparation Example B205

[0092] The methods for modifying the amino functional groups of zeolite molecular sieves are as follows:

[0093] (1) Acid washing: 10g of Y-type zeolite molecular sieve was added to 100ml of 0.3mol / L hydrochloric acid solution and heat-treated for 10h under stirring and reflux to remove metal cations; then the powder was filtered, washed and dried to obtain H+ type zeolite molecular sieve.

[0094] (2) Surface modification of amino functional groups: 10g of H+ type zeolite molecular sieve was added to 100ml of toluene solvent, followed by 0.04g of aminopropyltrimethoxysilane, 150uL of concentrated hydrochloric acid and 350uL of glacial acetic acid. The mixture was stirred and reacted under reflux at 110℃ for 12h. The powder was then filtered, washed and dried to obtain zeolite molecular sieve modified with amino functional groups.

[0095] Preparation Example B206

[0096] The methods for modifying the amino functional groups of zeolite molecular sieves are as follows:

[0097] (1) Acid washing: 10g of mordenite molecular sieve was added to 100ml of 0.1mol / L hydrochloric acid solution and heat-treated for 10h under stirring and reflux to remove metal cations; then the powder was filtered, washed and dried to obtain H+ type zeolite molecular sieve.

[0098] (2) Surface modification of amino functional groups: 10g of H+ type zeolite molecular sieve was added to 100ml of toluene solvent, followed by 0.02g of aminopropyltrimethoxysilane, 150uL of concentrated hydrochloric acid and 350uL of glacial acetic acid. The mixture was stirred and reacted under reflux at 110℃ for 12h. The powder was then filtered, washed and dried to obtain zeolite molecular sieve modified with amino functional groups.

[0099] Preparation Example B207

[0100] The methods for modifying the amino functional groups of zeolite molecular sieves are as follows:

[0101] (1) Acid washing: 10g of ZSM-5(MFI) zeolite molecular sieve was added to 100ml of 0.5mol / L hydrochloric acid solution and heat-treated for 12h under stirring and reflux to remove metal cations; then the powder was filtered, washed and dried to obtain H+ type zeolite molecular sieve.

[0102] (2) Surface modification of amino functional groups: 10g of H+ type zeolite molecular sieve was added to 100ml of toluene solvent, followed by 0.04g of aminopropyltrimethoxysilane, 150uL of concentrated hydrochloric acid and 350uL of glacial acetic acid. The mixture was stirred and reacted under reflux at 110℃ for 12h. The powder was then filtered, washed and dried to obtain zeolite molecular sieve modified with amino functional groups.

[0103] Preparation Example B208

[0104] The methods for modifying the amino functional groups of zeolite molecular sieves are as follows:

[0105] (1) Acid washing: 10g of ZSM-11(MEL) zeolite molecular sieve was added to 100ml of 0.8mol / L hydrochloric acid solution and heat-treated for 6h under stirring and reflux to remove metal cations; then the powder was filtered, washed and dried to obtain H+ type zeolite molecular sieve.

[0106] (2) Surface modification of amino functional groups: 10g of H+ type zeolite molecular sieve was added to 100ml of toluene solvent, followed by 0.04g of aminopropyltrimethoxysilane, 150uL of concentrated hydrochloric acid and 350uL of glacial acetic acid. The mixture was stirred and reacted under reflux at 110℃ for 12h. The powder was then filtered, washed and dried to obtain zeolite molecular sieve modified with amino functional groups.

[0107] Preparation Example B209

[0108] The methods for modifying the amino functional groups of zeolite molecular sieves are as follows:

[0109] (1) Acid washing: 10g of ZSM-8 zeolite molecular sieve was added to 100ml of 1mol / L hydrochloric acid solution and heat-treated for 6h under stirring and reflux to remove metal cations; then the powder was filtered, washed and dried to obtain H+ type zeolite molecular sieve.

[0110] (2) Surface modification of amino functional groups: 10g of H+ type zeolite molecular sieve was added to 100ml of toluene solvent, followed by 0.08g of aminopropyltrimethoxysilane, 150uL of concentrated hydrochloric acid and 350uL of glacial acetic acid. The mixture was stirred and reacted under reflux at 110℃ for 12h. The powder was then filtered, washed and dried to obtain zeolite molecular sieve modified with amino functional groups.

[0111] Preparation Example B210

[0112] The methods for modifying the amino functional groups of zeolite molecular sieves are as follows:

[0113] (1) Acid washing: 10g of ZSM-48 zeolite molecular sieve was added to 100ml of 1mol / L hydrochloric acid solution and heat-treated for 4h under stirring and reflux to remove metal cations; then the powder was filtered, washed and dried to obtain H+ type zeolite molecular sieve.

[0114] (2) Surface modification of amino functional groups: 10g of H+ type zeolite molecular sieve was added to 100ml of toluene solvent, followed by 0.02g of aminopropyltrimethoxysilane, 150uL of concentrated hydrochloric acid and 350uL of glacial acetic acid. The mixture was stirred and reacted under reflux at 110℃ for 12h. The powder was then filtered, washed and dried to obtain zeolite molecular sieve modified with amino functional groups.

[0115] Preparation Example B211

[0116] The methods for modifying the amino functional groups of zeolite molecular sieves are as follows:

[0117] (1) Acid washing: 10g of ZSM-35 zeolite molecular sieve was added to 100ml of 0.1mol / L hydrochloric acid solution and heat-treated for 12h under stirring and reflux to remove metal cations; then the powder was filtered, washed and dried to obtain H+ type zeolite molecular sieve.

[0118] (2) Surface modification of amino functional groups: 10g of H+ type zeolite molecular sieve was added to 100ml of toluene solvent, followed by 0.04g of aminopropyltrimethoxysilane, 150uL of concentrated hydrochloric acid and 350uL of glacial acetic acid. The mixture was stirred and reacted under reflux at 110℃ for 12h. The powder was then filtered, washed and dried to obtain zeolite molecular sieve modified with amino functional groups.

[0119] Preparation Example B212

[0120] The methods for modifying the amino functional groups of zeolite molecular sieves are as follows:

[0121] (1) Acid washing: 10g of β molecular sieve (BEA) was added to 100ml of 0.5mol / L hydrochloric acid solution and heat-treated for 12h under stirring and reflux to remove metal cations; then the powder was filtered, washed and dried to obtain H+ type zeolite molecular sieve.

[0122] (2) Surface modification of amino functional groups: 10g of H+ type zeolite molecular sieve was added to 100ml of toluene solvent, followed by 0.08g of aminopropyltrimethoxysilane, 150uL of concentrated hydrochloric acid and 350uL of glacial acetic acid. The mixture was stirred and reacted under reflux at 110℃ for 12h. The powder was then filtered, washed and dried to obtain zeolite molecular sieve modified with amino functional groups.

[0123] Preparation Example B213

[0124] The methods for modifying the amino functional groups of zeolite molecular sieves are as follows:

[0125] (1) Acid washing: 10g of 13X molecular sieve was added to 100ml of 0.1mol / L hydrochloric acid solution and heat-treated for 6h under stirring and reflux to remove metal cations; then the powder was filtered, washed and dried to obtain H+ type zeolite molecular sieve.

[0126] (2) Surface modification of amino functional groups: 10g of H+ type zeolite molecular sieve was added to 100ml of toluene solvent, followed by 0.04g of aminopropyltrimethoxysilane, 150uL of concentrated hydrochloric acid and 350uL of glacial acetic acid. The mixture was stirred and reacted under reflux at 110℃ for 12h. The powder was then filtered, washed and dried to obtain zeolite molecular sieve modified with amino functional groups.

[0127] Preparation Example B214

[0128] The methods for modifying the amino functional groups of zeolite molecular sieves are as follows:

[0129] (1) Acid washing: 10g of Silicalite-1 molecular sieve was added to 100ml of 1mol / L hydrochloric acid solution and heat-treated for 12h under stirring and reflux to remove metal cations; then the powder was filtered, washed and dried to obtain H+ type zeolite molecular sieve.

[0130] (2) Surface modification of amino functional groups: 10g of H+ type zeolite molecular sieve was added to 100ml of toluene solvent, followed by 0.02g of aminopropyltrimethoxysilane, 150uL of concentrated hydrochloric acid and 350uL of glacial acetic acid. The mixture was stirred and reacted under reflux at 110℃ for 12h. The powder was then filtered, washed and dried to obtain zeolite molecular sieve modified with amino functional groups.

[0131] Preparation Example B215

[0132] The methods for modifying the amino functional groups of zeolite molecular sieves are as follows:

[0133] (1) Acid washing: 10g of SSZ-23(STT) zeolite molecular sieve was added to 100ml of 0.3mol / L hydrochloric acid solution and heat-treated for 4h under stirring and reflux to remove metal cations; then the powder was filtered, washed and dried to obtain H+ type zeolite molecular sieve.

[0134] (2) Surface modification of amino functional groups: 10g of H+ type zeolite molecular sieve was added to 100ml of toluene solvent, followed by 0.04g of aminopropyltrimethoxysilane, 150uL of concentrated hydrochloric acid and 350uL of glacial acetic acid. The mixture was stirred and reacted under reflux at 110℃ for 12h. The powder was then filtered, washed and dried to obtain zeolite molecular sieve modified with amino functional groups.

[0135] The performance indicators of the zeolite molecular sieve raw materials used and the content of amino functional groups on their surface after treatment are shown in Table 1 below:

[0136] Table 1

[0137]

[0138]

[0139] Preparation Example C201

[0140] The treatment method for zeolite molecular sieves without amino functional group surface modification is as follows:

[0141] 10g of ZSM-11(MEL) zeolite molecular sieve to be treated was added to 100ml of 0.8mol / L hydrochloric acid or nitric acid solution and heat-treated under stirring and reflux for 6h to completely remove metal cations; then the powder was filtered, washed, and dried to obtain H + Type zeolite molecular sieve; for later use.

[0142] Preparation example C202

[0143] The treatment method for zeolite molecular sieves without amino functional group surface modification is as follows:

[0144] 10g of the NaA-type zeolite molecular sieve to be treated was added to 100ml of 0.5mol / L hydrochloric acid or nitric acid solution and heat-treated under stirring and reflux for 8h to completely remove metal cations; then the powder was filtered, washed, and dried to obtain H + Type zeolite molecular sieve; for later use.

[0145] The zeolite molecular sieves used without amino functional group surface modification are shown in Table 2 below:

[0146] Table 2

[0147]

[0148] The raw material information used in the embodiments and comparative examples of this invention is shown in Table 3 below:

[0149] Table 3

[0150]

[0151]

[0152] Example 1

[0153] The preparation method of polyimide composite resin film is as follows:

[0154] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 1.27 g of the amino-functionalized surface-modified ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208], 7.13 g of TFMB, and 3.85 g of HFBAPP were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 13.06 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0155] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 51 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0156] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a polyamic acid dry film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the carrier surface by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm. The structure of the polyimide composite resin is as follows:

[0157]

[0158] m+n=99, m=99, n=0, m / (m+n)=1.

[0159] Example 2

[0160] The preparation method of polyimide composite resin film is as follows:

[0161] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 1.27 g of the amino-functionalized surface-modified ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208], 5.50 g of TFMB, and 3.44 g of 4,4'-ODA were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 15.11 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0162] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 51 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0163] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0164] Example 3

[0165] The preparation method of polyimide composite resin film is as follows:

[0166] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 1.27 g of ZSM-11 (MEL) zeolite molecular sieve with amino functional groups modified in Preparation Example B208, 6.07 g of TFMB, and 3.80 g of 4,4'-ODA were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 8.42 g of 6FDA and 5.76 g of s-ODPA were added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain a polyamic acid solution.

[0167] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 51 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0168] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0169] Example 4

[0170] The preparation method of polyimide composite resin film is as follows:

[0171] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 1.27 g of the amino-functionalized surface-modified ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208] and 7.52 g of 4,4'-ODA were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compound in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere, and 16.53 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compound, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0172] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 51 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0173] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0174] Example 5

[0175] The preparation method of polyimide composite resin film is as follows:

[0176] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 1.27 g of the amino-functionalized surface-modified ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208] and 8.38 g of 4,4'-ODA were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compound in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 9.30 g of 6FDA and 6.36 g of s-ODPA were added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compound, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0177] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 51 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0178] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0179] Example 6

[0180] The preparation method of polyimide composite resin film is as follows:

[0181] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.73 g of the amino-functionalized surface-modified ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208], 7.13 g of TFMB, and 3.85 g of HFBAPP were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 13.06 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0182] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the thickness of the wet film is 53 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0183] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0184] Example 7

[0185] The preparation method of polyimide composite resin film is as follows:

[0186] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.48 g of the amino-functionalized surface-modified ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208], 7.13 g of TFMB, and 3.85 g of HFBAPP were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25°C under a nitrogen atmosphere. 13.06 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25°C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0187] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the thickness of the wet film is 53 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0188] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0189] Example 8

[0190] The preparation method of polyimide composite resin film is as follows:

[0191] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.25 g of the amino-functionalized surface-modified ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208], 7.13 g of TFMB, and 3.85 g of HFBAPP were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 13.06 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0192] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the thickness of the wet film is 53 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0193] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0194] Example 9

[0195] The preparation method of polyimide composite resin film is as follows:

[0196] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.14 g of the amino-functionalized surface-modified ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208], 7.13 g of TFMB, and 3.85 g of HFBAPP were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 13.06 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0197] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the thickness of the wet film is 53 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0198] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0199] Example 10

[0200] The preparation method of polyimide composite resin film is as follows:

[0201] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 1.27 g of the amino-functionalized surface-modified Y-type zeolite molecular sieve from [Preparation Example B205], 7.13 g of TFMB, and 3.85 g of HFBAPP were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 13.06 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0202] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 51 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0203] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0204] Example 11

[0205] The preparation method of polyimide composite resin film is as follows:

[0206] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 1.27 g of the amino-functionalized surface-modified 13X molecular sieve from [Preparation Example B213], 7.13 g of TFMB, and 3.85 g of HFBAPP were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 13.06 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0207] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 51 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0208] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0209] Example 12

[0210] The preparation method of polyimide composite resin film is as follows:

[0211] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.49 g of the amino-functionalized surface-modified ZSM-5 (MFI) zeolite molecular sieve from [Preparation Example B207] and 11.09 g of TFMB were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 7.69 g of 6FDA and 5.26 g of s-ODPA were added to the solution in three portions, each representing 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0212] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the thickness of the wet film is 53 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0213] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0214] Example 13

[0215] The preparation method of polyimide composite resin film is as follows:

[0216] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 1.27 g of the amino-functionalized surface-modified ZSM-35 zeolite molecular sieve from [Preparation Example B211], 7.13 g of TFMB, and 3.85 g of HFBAPP were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 13.06 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0217] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 51 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0218] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0219] Example 14

[0220] The preparation method of polyimide composite resin film is as follows:

[0221] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 1.27 g of the amino-functionalized surface-modified ZSM-8 zeolite molecular sieve from [Preparation Example B209], 7.13 g of TFMB, and 3.85 g of HFBAPP were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 13.06 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0222] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 51 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0223] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0224] Example 15

[0225] The preparation method of polyimide composite resin film is as follows:

[0226] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 1.27 g of the amino-functionalized surface-modified ZSM-48 zeolite molecular sieve from [Preparation Example B210], 7.13 g of TFMB, and 3.85 g of HFBAPP were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 13.06 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0227] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 51 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0228] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0229] Example 16

[0230] The preparation method of polyimide composite resin film is as follows:

[0231] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 1.27 g of the amino-functionalized surface-modified CaA type zeolite molecular sieve from [Preparation Example B203], 7.13 g of TFMB, and 3.85 g of HFBAPP were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 13.06 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0232] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 51 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0233] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0234] Example 17

[0235] The preparation method of polyimide composite resin film is as follows:

[0236] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.39 g of the amino-functionalized surface-modified NaA-type zeolite molecular sieve from [Preparation Example B202], 0.63 g of 4,4'-ODA, 1.39 g of TPE-R, and 4.10 g of HFBAPP were dispersed in 87 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 5 °C under a nitrogen atmosphere, and 6.88 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 5 °C, and the reaction was carried out under a nitrogen atmosphere for 48 h to obtain the polyamic acid solution.

[0237] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 100 μm; then it is evaporated at 120 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0238] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 280°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0239] Example 18

[0240] The preparation method of polyimide composite resin film is as follows:

[0241] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.39 g of the amino-functionalized surface-modified NaA-type zeolite molecular sieve from [Preparation Example B202], 0.63 g of 4,4'-ODA, 1.39 g of TPE-R, and 4.10 g of HFBAPP were dispersed in 87 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 5 °C under a nitrogen atmosphere, and 6.88 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 5 °C, and the reaction was carried out under a nitrogen atmosphere for 48 h to obtain the polyamic acid solution.

[0242] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 150 μm; then it is evaporated at 120 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0243] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 280°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 15µm.

[0244] Example 19

[0245] The preparation method of polyimide composite resin film is as follows:

[0246] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.39 g of the amino-functionalized surface-modified NaA-type zeolite molecular sieve from [Preparation Example B202], 0.63 g of 4,4'-ODA, 1.39 g of TPE-R, and 4.10 g of HFBAPP were dispersed in 87 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 5 °C under a nitrogen atmosphere, and 6.88 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 5 °C, and the reaction was carried out under a nitrogen atmosphere for 48 h to obtain the polyamic acid solution.

[0247] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 200 μm; then it is evaporated at 120 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0248] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 280°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 20 μm.

[0249] Example 20

[0250] The preparation method of polyimide composite resin film is as follows:

[0251] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.39 g of the amino-functionalized surface-modified NaA-type zeolite molecular sieve from [Preparation Example B202], 0.63 g of 4,4'-ODA, 1.39 g of TPE-R, and 4.10 g of HFBAPP were dispersed in 87 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 5 °C under a nitrogen atmosphere, and 6.88 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 5 °C, and the reaction was carried out under a nitrogen atmosphere for 48 h to obtain the polyamic acid solution.

[0252] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 250 μm; then it is evaporated at 120 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0253] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 280°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 25 μm.

[0254] Example 21

[0255] The preparation method of polyimide composite resin film is as follows:

[0256] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.39 g of the amino-functionalized surface-modified NaA-type zeolite molecular sieve from [Preparation Example B202], 0.63 g of 4,4'-ODA, 1.39 g of TPE-R, and 4.10 g of HFBAPP were dispersed in 87 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 5 °C under a nitrogen atmosphere, and 6.88 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 5 °C, and the reaction was carried out under a nitrogen atmosphere for 48 h to obtain the polyamic acid solution.

[0257] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 300 μm; then it is evaporated at 120 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0258] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 280°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 30 μm.

[0259] Example 22

[0260] The preparation method of polyimide composite resin film is as follows:

[0261] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.49 g of the amino-functionalized surface-modified NaA-type zeolite molecular sieve from [Preparation Example B202], 0.63 g of 4,4'-ODA, 1.39 g of TPE-R, and 4.10 g of HFBAPP were dispersed in 87 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 5 °C under a nitrogen atmosphere, and 6.88 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 5 °C, and the reaction was carried out under a nitrogen atmosphere for 48 h to obtain the polyamic acid solution.

[0262] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 100 μm; then it is evaporated at 120 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0263] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 280°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0264] Example 23

[0265] The preparation method of polyimide composite resin film is as follows:

[0266] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.68 g of the amino-functionalized surface-modified NaA-type zeolite molecular sieve from [Preparation Example B202], 0.63 g of 4,4'-ODA, 1.39 g of TPE-R, and 4.10 g of HFBAPP were dispersed in 87 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 5 °C under a nitrogen atmosphere, and 6.88 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 5 °C, and the reaction was carried out under a nitrogen atmosphere for 48 h to obtain the polyamic acid solution.

[0267] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 100 μm; then it is evaporated at 120 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0268] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 280°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0269] Example 24

[0270] The preparation method of polyimide composite resin film is as follows:

[0271] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.39 g of the amino-functionalized surface-modified ZSM-35 zeolite molecular sieve from [Preparation Example B211], 0.63 g of 4,4'-ODA, 1.39 g of TPE-R, and 4.10 g of HFBAPP were dispersed in 87 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 5 °C under a nitrogen atmosphere, and 6.88 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 5 °C, and the reaction was carried out under a nitrogen atmosphere for 48 h to obtain the polyamic acid solution.

[0272] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 100 μm; then it is evaporated at 120 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0273] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 280°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0274] Example 25

[0275] The preparation method of polyimide composite resin film is as follows:

[0276] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.39 g of SSZ-23 (STT) zeolite molecular sieve with amino functional groups modified in Preparation Example B215, 0.63 g of 4,4'-ODA, 1.39 g of TPE-R, and 4.10 g of HFBAPP were dispersed in 87 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 5 °C under a nitrogen atmosphere, and 6.88 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 5 °C, and the reaction was carried out under a nitrogen atmosphere for 48 h to obtain a polyamic acid solution.

[0277] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 100 μm; then it is evaporated at 120 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0278] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 280°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0279] Example 26

[0280] The preparation method of polyimide composite resin film is as follows:

[0281] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.39 g of the amino-functionalized surface-modified KA-type zeolite molecular sieve from [Preparation Example B201], 0.63 g of 4,4'-ODA, 1.39 g of TPE-R, and 4.10 g of HFBAPP were dispersed in 87 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 5 °C under a nitrogen atmosphere, and 6.88 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 5 °C, and the reaction was carried out under a nitrogen atmosphere for 48 h to obtain the polyamic acid solution.

[0282] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 100 μm; then it is evaporated at 120 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0283] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 280°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0284] Example 27

[0285] The preparation method of polyimide composite resin film is as follows:

[0286] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.87 g of amino-functionalized surface-modified mordenite molecular sieve from [Preparation Example B206], 2.69 g of 4,4'-MDA, and 4.35 g of TFMB were dispersed in 82 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 45 °C under a nitrogen atmosphere. 2.53 g of s-ODPA, 2.40 g of BPADA, and 6.03 g of 6FDA were added to the solution in three portions, each representing 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 45 °C, and the reaction was carried out under a nitrogen atmosphere for 4 h to obtain a polyamic acid solution.

[0287] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 70 μm; then it is evaporated at 80 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 25 wt%.

[0288] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 320°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0289] Example 28

[0290] The preparation method of polyimide composite resin film is as follows:

[0291] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.87 g of the amino-functionalized surface-modified Silicalite-1 molecular sieve from [Preparation Example B214], 2.69 g of 4,4'-MDA, and 4.35 g of TFMB were dispersed in 82 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 45 °C under a nitrogen atmosphere. 2.53 g of s-ODPA, 2.40 g of BPADA, and 6.03 g of 6FDA were added to the solution in three portions, each representing 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 45 °C, and the reaction was carried out under a nitrogen atmosphere for 4 h to obtain the polyamic acid solution.

[0292] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 70 μm; then it is evaporated at 80 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 25 wt%.

[0293] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 320°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0294] Example 29

[0295] The preparation method of polyimide composite resin film is as follows:

[0296] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.87 g of the amino-functionalized surface-modified β-zeolite (BEA) from [Preparation Example B212], 2.69 g of 4,4'-MDA, and 4.35 g of TFMB were dispersed in 82 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 45 °C under a nitrogen atmosphere. 2.53 g of s-ODPA, 2.40 g of BPADA, and 6.03 g of 6FDA were added to the solution in three portions, each representing 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 45 °C, and the reaction was carried out under a nitrogen atmosphere for 4 h to obtain the polyamic acid solution.

[0297] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 70 μm; then it is evaporated at 80 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 25 wt%.

[0298] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 320°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0299] Example 30

[0300] The preparation method of polyimide composite resin film is as follows:

[0301] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.73 g of the amino-functionalized surface-modified Y-type zeolite molecular sieve from [Preparation Example B205], 0.59 g of p-PDA, and 5.44 g of TFMB were dispersed in 85 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 45 °C under a nitrogen atmosphere. 1.33 g of s-BPDA and 7.64 g of 6FDA were added to the solution in three portions, each representing 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 45 °C, and the reaction was carried out under a nitrogen atmosphere for 12 h to obtain the polyamic acid solution.

[0302] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the thickness of the wet film is 130 μm; then it is evaporated at 100 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0303] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 300°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 15µm.

[0304] Example 31

[0305] The preparation method of polyimide composite resin film is as follows:

[0306] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.21 g of the amino-functionalized surface-modified X-type zeolite molecular sieve from [Preparation Example B204], 0.59 g of p-PDA, and 5.44 g of TFMB were dispersed in 85 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 45 °C under a nitrogen atmosphere. 1.33 g of s-BPDA and 7.64 g of 6FDA were added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 45 °C, and the reaction was carried out under a nitrogen atmosphere for 12 h to obtain the polyamic acid solution.

[0307] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the thickness of the wet film is 130 μm; then it is evaporated at 100 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0308] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 300°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 15µm.

[0309] Example 32

[0310] The preparation method of polyimide composite resin film is as follows:

[0311] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.68 g of the amino-functionalized surface-modified ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208], 0.63 g of 4,4'-ODA, 1.39 g of TPE-R, and 4.10 g of HFBAPP were dispersed in 87 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 5 °C under a nitrogen atmosphere, and 6.88 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 5 °C, and the reaction was carried out under a nitrogen atmosphere for 48 h to obtain the polyamic acid solution.

[0312] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 100 μm; then it is evaporated at 120 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0313] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 280°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0314] Example 33

[0315] The preparation method of polyimide composite resin film is as follows:

[0316] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.95 g of the amino-functionalized surface-modified ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208], 2.69 g of 4,4'-MDA, and 4.35 g of TFMB were dispersed in 82 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 45 °C under a nitrogen atmosphere. 2.53 g of s-ODPA, 2.40 g of BPADA, and 6.03 g of 6FDA were added to the solution in three portions, each representing 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 45 °C, and the reaction was carried out under a nitrogen atmosphere for 4 h to obtain the polyamic acid solution.

[0317] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 70 μm; then it is evaporated at 80 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 25 wt%.

[0318] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 320°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0319] Example 34

[0320] The preparation method of polyimide composite resin film is as follows:

[0321] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.79 g of the amino-functionalized surface-modified ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208], 0.59 g of p-PDA, and 5.44 g of TFMB were dispersed in 85 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 45 °C under a nitrogen atmosphere. 1.33 g of s-BPDA and 7.64 g of 6FDA were added to the solution in three portions, each representing 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 45 °C, and the reaction was carried out under a nitrogen atmosphere for 12 h to obtain the polyamic acid solution.

[0322] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 87 μm; then it is evaporated at 100 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0323] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 300°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0324] Example 35

[0325] The preparation method of polyimide composite resin film is as follows:

[0326] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 1.05 g of the amino-functionalized surface-modified ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208], 2.14 g of m-TD, and 6.21 g of BAPP were dispersed in 80 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 15 °C under a nitrogen atmosphere. 6.04 g of BPADA and 5.60 g of 6FDA were added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 15 °C, and the reaction was carried out under a nitrogen atmosphere for 48 h to obtain the polyamic acid solution.

[0327] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the thickness of the wet film is 63 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0328] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0329] Example 36

[0330] The preparation method of polyimide composite resin film is as follows:

[0331] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.95 g of the amino-functionalized surface-modified ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208] and 9.57 g of BAPP were dispersed in 82 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 0.36 g of PMDA, 2.89 g of s-ODPA, and 5.18 g of 6FDA were added to the solution in three portions, each representing 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 12 h to obtain the polyamic acid solution.

[0332] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 68 μm; then it is evaporated at 120 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0333] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 320°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0334] Comparative Example 1

[0335] The preparation method of polyimide composite resin film is as follows:

[0336] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 1.27 g of ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example C201], 7.13 g of TFMB, and 3.85 g of HFBAPP were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 13.06 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0337] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 51 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0338] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0339] Comparative Example 2

[0340] The preparation method of polyimide composite resin film is as follows:

[0341] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.39 g of NaA-type zeolite molecular sieve from [Preparation Example C202], 0.63 g of 4,4'-ODA, 1.39 g of TPE-R, and 4.10 g of HFBAPP were dispersed in 87 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 5°C under a nitrogen atmosphere, and 6.88 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 5°C, and the reaction was carried out under a nitrogen atmosphere for 48 h to obtain a polyamic acid solution.

[0342] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 100 μm; then it is evaporated at 120 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0343] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 280°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0344] Comparative Example 3

[0345] The preparation method of polyimide composite resin film is as follows:

[0346] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.79 g of ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208], 3.00 g of p-PDA, and 1.85 g of 4,4'-ODA were dispersed in 85 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 1.45 g of PMDA and 8.70 g of s-BPDA were added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 12 h to obtain a polyamic acid solution.

[0347] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 84 μm; then it is evaporated at 100 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 25 wt%.

[0348] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 320°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0349] Comparative Example 4

[0350] The preparation method of polyimide composite resin film is as follows:

[0351] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.79 g of ZSM-11 (MEL) zeolite molecular sieve (from Preparation Example B208), 0.51 g of 4,4'-ODA, and 6.72 g of TPE-R were dispersed in 85 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 35 °C under a nitrogen atmosphere. 7.77 g of s-ODPA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 35 °C, and the reaction was carried out under a nitrogen atmosphere for 12 h to obtain a polyamic acid solution.

[0352] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 85 μm; then it is evaporated at 80 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 25 wt%.

[0353] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0354] Comparative Example 5

[0355] The preparation method of polyimide composite resin film is as follows:

[0356] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 7.13 g TFMB and 3.85 g HFBAPP were dispersed in 76 g NMP solvent in a container with stirring to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 13.06 g 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0357] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 55 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0358] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0359] Comparative Example 6

[0360] The preparation method of polyimide composite resin film is as follows:

[0361] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.63 g of 4,4'-ODA, 1.39 g of TPE-R, and 4.10 g of HFBAPP were dispersed in 87 g of NMP solvent while stirring in a container to ensure complete dissolution of the diamine compounds in the solution. The solution temperature was controlled at 5 °C under a nitrogen atmosphere. 6.88 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 5 °C, and the reaction was carried out under a nitrogen atmosphere for 48 h to obtain the polyamic acid solution.

[0362] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 100 μm; then it is evaporated at 120 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0363] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 280°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0364] Comparative Example 7

[0365] The preparation method of polyimide composite resin film is as follows:

[0366] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 2.69 g of 4,4'-MDA and 4.35 g of TFMB were dispersed in 82 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 45 °C under a nitrogen atmosphere. 2.53 g of s-ODPA, 2.40 g of BPADA, and 6.03 g of 6FDA were added to the solution in three portions, each representing 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 45 °C, and the reaction was carried out under a nitrogen atmosphere for 4 hours to obtain the polyamic acid solution.

[0367] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 70 μm; then it is evaporated at 80 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 25 wt%.

[0368] (3) Obtaining polyimide film by heat treatment: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 320°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 9 μm.

[0369] Example 37

[0370] The preparation method of polyimide composite resin film is as follows:

[0371] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 1.61 g of the amino-functionalized surface-modified ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208], 7.13 g of TFMB, and 3.85 g of HFBAPP were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 13.06 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0372] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the thickness of the wet film is 53 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0373] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0374] Example 38

[0375] The preparation method of polyimide composite resin film is as follows:

[0376] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.07 g of the amino-functionalized surface-modified ZSM-11 (MEL) zeolite molecular sieve from [Preparation Example B208], 7.13 g of TFMB, and 3.85 g of HFBAPP were dispersed in 76 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 13.06 g of 6FDA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 24 h to obtain the polyamic acid solution.

[0377] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the thickness of the wet film is 53 μm; then it is evaporated at 150 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 15 wt%.

[0378] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0379] Comparative Example 8

[0380] The preparation method of polyimide composite resin film is as follows:

[0381] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 9.57 g of BAPP was dispersed in 82 g of NMP solvent while stirring in a container to completely dissolve the diamine compound in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 0.36 g of PMDA, 2.89 g of s-ODPA, and 5.18 g of 6FDA were added to the solution in three portions, each representing 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compound, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 12 h to obtain the polyamic acid solution.

[0382] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 68 μm; then it is evaporated at 120 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 20 wt%.

[0383] (3) Obtaining polyimide film by heat treatment: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 320°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 9 μm.

[0384] Comparative Example 9

[0385] The preparation method of polyimide composite resin film is as follows:

[0386] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 3.00 g of p-PDA and 1.85 g of 4,4'-ODA were dispersed in 85 g of NMP solvent while stirring in a container to completely dissolve the diamine compounds in the solution. The solution temperature was controlled at 25 °C under a nitrogen atmosphere. 1.45 g of PMDA and 8.70 g of s-BPDA were added to the solution in three portions, each representing 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compounds, respectively. The solution temperature was then controlled at 25 °C, and the reaction was carried out under a nitrogen atmosphere for 12 h to obtain the polyamic acid solution.

[0387] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 84 μm; then it is evaporated at 100 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 25 wt%.

[0388] (3) Obtaining polyimide film by heat treatment: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 320°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 9 μm.

[0389] Comparative Example 10

[0390] The preparation method of polyimide composite resin film is as follows:

[0391] (1) Preparation of polyamic acid solution: Under a nitrogen atmosphere, 0.51 g of 4,4'-ODA and 6.72 g of TPE-R were dispersed in 85 g of NMP solvent while stirring in a container to completely dissolve the diamine compound in the solution. The solution temperature was controlled at 35 °C under a nitrogen atmosphere. 7.77 g of s-ODPA was added to the solution in three portions, each time accounting for 60%, 30%, and 10% of the total weight of the tetracarboxylic dianhydride compound, respectively. The solution temperature was then controlled at 35 °C, and the reaction was carried out under a nitrogen atmosphere for 12 h to obtain the polyamic acid solution.

[0392] (2) Coating of polyamic acid solution: The polyamic acid solution prepared in step (1) is coated on a glass plate carrier, and the wet film thickness is 85 μm; then it is evaporated at 80 °C to obtain a polyamic acid dry film layer, and the content of strong polar solvent in the dry film layer is between 25 wt%.

[0393] (3) Heat treatment to obtain polyimide film: In a nitrogen atmosphere, the carrier coated with a dry polyamic acid film layer is heat-treated in an oven at 350°C; the polyamic acid undergoes an imidization reaction to obtain a polyimide film layer; the polyimide film is peeled off from the surface of the carrier by boiling in water to obtain a zeolite molecular sieve modified polyimide composite resin film product. The film thickness is 10 μm.

[0394] (1) Gas separation performance of polyimide composite resin film. Gas separation performance was tested using a VAC-V2 differential pressure gas permeation apparatus. The film sample, dried at 150℃ for 0.5h, was placed between the upper and lower test chambers and clamped. The low-pressure chamber was evacuated, and then the entire system was evacuated. The low-pressure chamber was then closed, and pure test gas at 1 atmosphere was introduced into the high-pressure chamber, ensuring a constant pressure difference across the sample. Under the influence of the pressure gradient, gas permeated from the high-pressure side to the low-pressure side. By monitoring the pressure on the low-pressure side, the barrier properties of the tested sample were determined. Test conditions: gas pressure 1 atmosphere, test temperature 30℃. The gas permeability coefficient P is measured in barrers, 1 barrer = 1 × 10⁻⁶. -10 cm 3 (STP)cm / cm 2 s cmHg, separation factor α=P A / P B .

[0395] (2) Tensile strength and elongation at break of polyimide composite resin film. The tensile strength and elongation at break of the polyimide composite resin film were tested using a universal tensile testing machine. The polyimide composite resin film sample was cut into strips of 20cm x 1cm. The film sample was fixed on a fixture, and an extensometer was clamped. The force range of the tensile fixture was 50N, and the tensile rate was 50.8mm / min. Data points at the point of fracture were selected to obtain the tensile strength and elongation at break results.

[0396] (3) Thickness of polyimide composite resin film. The thickness of polyimide composite resin film was tested using a micrometer.

[0397] The properties of the polyimide composite resin films in the embodiments and comparative examples of the present invention are shown in Table 4 below.

[0398] Table 4

[0399]

[0400]

[0401] Note: The CO2 / CH4 separation factor is the quotient of the CO2 permeability coefficient and the CH4 permeability coefficient. Due to the rounding of the permeability coefficient, the values ​​are not completely corresponding and there are slight differences.

[0402] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A composite resin, characterized in that, The composite resin includes: Polyimide has the following structure: Wherein, 500≥m+n≥20; 0.5≤m / (m+n)≤1, m and n are natural numbers, Ar is a dianhydride residue that is not 6FDA, B is a diamine residue, the diamine includes fluoroalkyl-substituted diamines, and the molar percentage of fluoroalkyl-substituted diamines in the diamine is not less than 50%; and, Zeolite molecular sieves with amino groups chemically bonded to their surface.

2. The composite resin according to claim 1, characterized in that, In the structure described, 300 ≥ m + n ≥ 20; 0.5 ≤ m / (m + n) ≤ 0.

8. The dianhydride includes at least one of the following: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-terephthalodioxydiphthalic anhydride, bisphenol A type diether dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride.

3. The composite resin according to claim 1 or 2, characterized in that, In the fluoroalkyl-substituted diamine, the fluoroalkyl group is a fluoroC1-C5 alkyl group, preferably a trifluoroC1-C5 alkyl group, and more preferably a trifluoromethyl group; The fluoroalkyl-substituted diamines include 2,2'-bis(trifluoromethyl)diaminobiphenyl and / or 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane; and / or The diamine may also contain other diamines, including at least one of p-phenylenediamine, m-phenylenediamine, benzidine, 4,4'-diaminobenzoylaniline, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, 1,3-bis(4'-aminophenoxy)benzene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,4-cyclohexanediamine, 1,6-hexanediamine, and polyetheramine D-2000, preferably at least two.

4. The composite resin according to any one of claims 1-3, characterized in that, The molar percentage of fluoroalkyl-substituted diamines in the diamine is 60-100%.

5. The composite resin according to any one of claims 1-4, characterized in that, The amino groups on the surface of the zeolite molecular sieve have a distribution density of 0.001-0.02 mmol / g, preferably 0.01-0.02 mmol / g; and / or The main channel pore size of the zeolite molecular sieve is 0.3-1.0 nm; and / or The zeolite molecular sieve has a particle size of 0.5-2.0 μm; and / or The specific surface area of ​​the zeolite molecular sieve is 400-1000 m². 2 / g.

6. The composite resin according to any one of claims 1-5, characterized in that, The zeolite molecular sieve includes at least one of the following: type A zeolite, type X zeolite, type Y zeolite, mordenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-8 zeolite, ZSM-48 zeolite, ZSM-35 zeolite, β molecular sieve, 13X molecular sieve, Silicalite-1 molecular sieve, and SSZ-23 zeolite.

7. The composite resin according to any one of claims 1-6, characterized in that, The zeolite molecular sieve has a weight percentage of 0.5-5.0% in the composite resin, and the polyimide has a weight percentage of 95-99.5% in the composite resin.

8. A method for preparing the composite resin according to any one of claims 1-7, characterized in that, The preparation method includes the following steps: (1) Preparation of polyamic acid solution, including: dispersing zeolite molecular sieve and diamine compound in solvent under inert atmosphere; adding dianhydride compound to solution for polymerization reaction; (2) Heat treatment, including: after removing part of the solvent from the polyamic acid solution, heat treatment is carried out in a nitrogen atmosphere.

9. The preparation method according to claim 8, characterized in that, The conditions for the polymerization reaction include: a temperature of 5-45°C; and / or a reaction time of 4-48 h; and / or The solid content of the polyamic acid solution is 10-25 wt%. and / or The solvent is a strongly polar solvent, preferably at least one of N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), and m-cresol.

10. The preparation method according to claim 8 or 9, characterized in that, The heat treatment temperature is 280-350℃.

11. The preparation method according to any one of claims 8-10, characterized in that, The preparation method of the zeolite molecular sieve includes: under solvent and catalyst conditions, H + The zeolite molecular sieve is contacted with aminopropyltrimethoxysilane; preferably, The contact conditions include: reflux at 110-120°C for 12-24 hours.

12. The application of the composite resin according to any one of claims 1-7 and / or the composite resin prepared by the preparation method according to any one of claims 8-11 in the preparation of gas separation membranes.

13. A gas separation membrane, characterized in that, The gas separation membrane comprises the composite resin according to any one of claims 1-7 and / or the composite resin prepared by the preparation method according to any one of claims 8-11.

14. The gas separation membrane according to claim 13, characterized in that, The thickness of the gas separation membrane is 10-30 μm.

15. The method for preparing the gas separation membrane according to claim 13 or 14, characterized in that, The method includes the following steps: (1) Preparation of polyamic acid solution, including: dispersing zeolite molecular sieve and diamine compound in solvent under nitrogen atmosphere; adding dianhydride compound to solution for polymerization reaction; (2) Coating film preparation, including: coating the polyamic acid solution of step (1) onto the carrier, desolventizing to a solvent content of 15-25 wt%, and obtaining a dry film; (3) Heat treatment, including: heat treatment of the dry film in a nitrogen atmosphere.

16. The application of the gas separation membrane according to claim 13 in the separation of CH4 / CO2 mixed gases.

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