Mixed matrix membranes containing high loading of zif-62 and their preparation and use

Abstract

The application provides a mixed matrix membrane containing high load ZIF-62 and a preparation and application thereof, and the preparation method comprises the following steps: S1, dispersing inherent microporous polymer PIM-1 and ZIF-62 in chloroform, uniformly and evenly laying the obtained mixed solution in a film forming device, then naturally evaporating, and then drying the obtained film forming material; S2, baking the film forming material after the drying treatment in S1 in an inert atmosphere, and obtaining the mixed matrix membrane containing high load ZIF-62 after the baking is completed. The mixed matrix membrane provided by the application is a kind of defect-free and high load composite film material, the load of the filler ZIF-62 is up to 80 wt%, and the propane / propylene separation ratio is higher, which indicates that the mixed matrix membrane can be used for the separation of propane and propylene mixed gas.

Description

TECHNICAL FIELD

[0001] The application relates to a mixed matrix membrane containing a high-loading glassy MOF and preparation and application thereof, in particular to a mixed matrix membrane containing a high-loading ZIF-62 and preparation and application thereof, and belongs to the field of membrane materials and separation technology. BACKGROUND

[0002] Compared with traditional gas separation methods, membrane separation strategies have attracted extensive attention due to low energy consumption, high efficiency and easy operation. In recent decades, due to the characteristics of low cost and easy manufacturing, high polymer membranes as a kind of commercial membrane materials have been widely studied and used in various industrial gas separation processes. However, the separation performance of the high polymer membranes is often limited by the Robeson upper limit (in traditional thin film gas separation, permeability and selectivity cannot be considered at the same time, and there is an upper limit, it is difficult to have high permeability and high selectivity at the same time), which means that there is always a balance between the flux and the selectivity of the high polymer membranes. The introduction of a porous filler into a polymer matrix to prepare a mixed matrix membrane (hereinafter referred to as MMMs) is an effective method to avoid this limitation. In theory, the separation performance of the MMMs will increase with the increase of the proportion of the porous filler. However, when the proportion of the porous filler is relatively high (more than 20wt%), the gap between the porous filler and the high polymer will reduce the separation performance, so the filler in the ideal MMMs should have good compatibility with the high polymer.

[0003] Compared to typical inorganic fillers, metal-organic frameworks (MOFs), based on their organic components, exhibit better interfacial compatibility with polymers and are considered promising filler materials. However, with increasing MOF loading in MMMs, the overestimated interfacial compatibility between MOFs and polymers, along with filler particle agglomeration, often leads to the formation of non-selective voids, resulting in actual membrane separation performance lower than predicted. Researchers have conducted extensive explorations to prepare high-loading and defect-free MOF-based MMMs. Based on the structural diversity of MOFs and the designable and tunable pore environment, surface modification of MOFs is the most common method for optimizing the filler / polymer interface to prepare high-loading MMMs. For example, Cohen et al. (ACS Appl. Mater. Interfaces 2019, 11, 13, 13029-13037) synthesized UiO-66-Alyl by covalently grafting polydimethylsiloxane (PDMS) onto the surface of UiO-66 particles via post-synthetic modification, and further synthesized defect-free 50 wt% MOF-loaded MMMs using modified UiO-66-Alyl. Compared with MMMs composed of unfunctionalized UiO-66, UiO-66-Alyl-based MMMs exhibited higher CO2 permeability without sacrificing selectivity. In addition, polymer modification, using MOF composites as fillers, adding interfacial agents, or in-situ synthesis of MOFs during MMM preparation are also important methods for obtaining high-performance and high-load MOF-based MMMs. Despite extensive exploration of synthetic methods, successful preparation of high-load (>50 wt%) defect-free MOF-based MMMs remains rare, and the preparation methods are generally complex.

[0004] Glass-transformed MOFs are considered promising candidates for membrane fabrication. This can be mainly attributed to two aspects: 1) the glass-transformed MOFs have a high melting temperature (T0). m ) and decomposition temperature (T) d Within the temperature range between 1 and 2, it exists in liquid form, which simplifies the membrane preparation process and, more importantly, enhances interfacial compatibility to reduce defects in the membrane material. 2) Although the MOF glass produced by the melting process cannot retain the long-range ordered characteristics of MOF materials, it still maintains porosity, which provides a good foundation for its application in gas separation and storage.

[0005] Therefore, providing a hybrid matrix membrane with a high loading of ZIF-62 and its preparation and application have become technical problems that urgently need to be solved in this field. Summary of the Invention

[0006] To address the aforementioned shortcomings and deficiencies, one objective of this invention is to provide a method for preparing a hybrid matrix membrane containing a high loading of ZIF-62.

[0007] Another object of the present invention is to provide a mixed matrix membrane containing a high loading of ZIF-62 prepared by the above-described method for preparing a mixed matrix membrane containing a high loading of ZIF-62.

[0008] Another object of the present invention is to provide the application of the above-described mixed matrix membrane containing a high loading of ZIF-62 in gas separation.

[0009] To achieve the above objectives, in one aspect, the present invention provides a method for preparing a hybrid matrix membrane containing a high loading of ZIF-62, wherein the preparation method includes:

[0010] S1: Disperse the inherently microporous polymers PIM-1 and ZIF-62 in chloroform, spread the resulting mixed solution (i.e. casting solution) evenly and evenly in the film-forming apparatus, then allow it to evaporate naturally, and then dry the resulting film-forming material to remove excess solvent.

[0011] S2: The film-forming material after drying in S1 is calcined in an inert atmosphere, and after calcination, the mixed matrix film containing high loading of ZIF-62 is obtained.

[0012] As a specific embodiment of the preparation method described above in this invention, in S1, the inherently microporous polymers PIM-1 and ZIF-62 are dispersed in chloroform, comprising:

[0013] S11: Dissolve ZIF-62 in chloroform and disperse it evenly;

[0014] S12: Dissolve the inherently microporous polymer PIM-1 in the dispersion obtained in S11 and disperse it uniformly to form a homogeneous mixed solution;

[0015] or;

[0016] 1): Dissolve the inherently microporous polymer PIM-1 in chloroform and disperse it uniformly to form solution A;

[0017] 2): Dissolve ZIF-62 in chloroform and disperse it evenly to form solution B;

[0018] 3): Mix solution A and solution B thoroughly to form a homogeneous mixed solution.

[0019] In a specific embodiment of the preparation method described above in this invention, in S1, the mass ratio between the inherently microporous polymer PIM-1 and ZIF-62 is 1:0-4, preferably 1:0.05-4.

[0020] As a specific embodiment of the preparation method described above in this invention, in S12, the inherently microporous polymer PIM-1 is dissolved in the dispersion obtained in S11 in batches and then uniformly dispersed; preferably, the batches are 3 batches; more preferably, when the inherently microporous polymer PIM-1 is dissolved in the dispersion obtained in S11 in 3 batches, the mass ratio of the inherently microporous polymer PIM-1 added in each batch is 1:2:7.

[0021] As a specific embodiment of the preparation method described above in this invention, the uniform dispersion in S11 and S12 can be achieved by ultrasonic dispersion and / or stirring.

[0022] As a specific embodiment of the preparation method described above in this invention, in step 3), the thorough mixing of liquid A and liquid B is to mix liquid B with liquid A in batches. Preferably, the batches are 3 batches. More preferably, when mixing liquid B with liquid A in 3 batches, the mass ratio of ZIF-62 added in each batch is controlled to be 1:2:7.

[0023] As a specific embodiment of the preparation method described above in this invention, the uniform dispersion in steps 1)-2) can be achieved by ultrasonic dispersion and / or stirring, and the thorough mixing in step 3) can also be achieved by ultrasonic dispersion and / or stirring.

[0024] The ZIF-62 and inherently microporous polymer PIM-1 used in this invention can be commercially available products or ZIF-62 and inherently microporous polymer PIM-1 prepared by conventional methods.

[0025] As a specific embodiment of the preparation method described above in this invention, in S1, the preparation method of the inherently microporous polymer PIM-1 includes:

[0026] TFTPN, TTSBI, anhydrous K2CO3 and anhydrous N,N-dimethylformamide were stirred and refluxed under a nitrogen atmosphere to obtain a reaction solution. After the reaction solution was cooled, it was slowly poured into methanol and filtered under vacuum to obtain a bright yellow solid.

[0027] The obtained bright yellow solid was dissolved in dichloromethane, filtered, and the filtrate was precipitated again in methanol. The solid product was obtained by vacuum filtration. This step was repeated.

[0028] The obtained solid was then washed and filtered, and finally dried in a vacuum drying oven to obtain a bright yellow product, which is the inherently microporous polymer PIM-1.

[0029] As a specific embodiment of the preparation method described above in this invention, in S1, the preparation method of the inherently microporous polymer PIM-1 specifically includes:

[0030] 1) Recrystallization of 5,5',6,6'-tetrahydroxy-3,3',3,3'-tetramethyl-1,1'-spirobisindane, i.e., TTSBI:

[0031] Dissolve the TTSBI to be purified in an appropriate amount of hot methanol, and further heat to evaporate about half of the solvent. Then slowly add dichloromethane dropwise to the solution until turbidity is produced. Let it stand for 2-3 hours, and obtain a white solid by vacuum filtration. Then dry the obtained white solid in a vacuum drying oven at 50-70℃ until the product quality no longer decreases, and obtain purified TTSBI.

[0032] 2) Purification of tetrafluoroterephthalonitrile, i.e., TFTPN:

[0033] Take an appropriate amount of TFTPN to be purified in a micro-sublimation apparatus, and sublimate the system under vacuum conditions at a temperature of 140-150℃ to obtain purified TFTPN.

[0034] 3) Polymerization reaction:

[0035] Purified TFTPN, purified TTSBI, and anhydrous K2CO3 in a molar ratio of 1-1.5:1-1.5:3-4.5 were added to a reactor. An appropriate amount of anhydrous N,N-dimethylformamide (DMF) was added under a nitrogen atmosphere. The mixture was stirred until the reactants were completely dissolved. The temperature was then raised to 40-80℃ and the reaction was maintained under a nitrogen atmosphere for 40-80 hours. After the reaction was completed, a viscous yellow solution was obtained.

[0036] 4) Post-processing:

[0037] After the reaction solution cools, slowly pour it into an appropriate amount of methanol. Obtain a bright yellow solid by vacuum filtration. Dissolve the obtained solid in dichloromethane, filter it, and then precipitate the filtrate again in methanol. Obtain the solid product by vacuum filtration. Repeat the above operation. Then wash and filter the obtained solid with ultrapure water. Finally, dry it in a vacuum drying oven at 70-80℃ for 12-24 hours to obtain a bright yellow product, which is the inherently microporous polymer PIM-1.

[0038] As a specific embodiment of the preparation method described above in this invention, the vacuum condition during the purification process of tetrafluoroterephthalonitrile, i.e., TFTPN, can be, for example, -0.02 MPa.

[0039] In one specific embodiment of the preparation method described above in this invention, during the polymerization reaction, the temperature is raised to 60-70°C and the reaction is maintained under a nitrogen atmosphere for 72-80 hours.

[0040] In one specific embodiment of the preparation method described above, the number of repetitions of the operation during post-processing can be reasonably adjusted according to actual operational needs. For example, in some embodiments of the present invention, the number of repetitions can be 2 or 3 times, etc.

[0041] As a specific embodiment of the preparation method described above in this invention, in S1, the preparation method of ZIF-62 includes:

[0042] A mixture of Zn(NO3)2·6H2O, imidazole, benzimidazole, and an appropriate amount of DMF in a mass ratio of 1-1.5:4.5-6:1-1.5 is stirred continuously at 25-100℃ for 10-14h (preferably 12-14h). The product is then collected by centrifugation and washed to remove unreacted reactants.

[0043] Preferably, the product is washed three times each with DMF and EtOH to remove unreacted reactants.

[0044] As a specific embodiment of the preparation method described above in this invention, in S1, the natural evaporation is natural evaporation at 10-30℃ for 10-14 hours.

[0045] In one specific embodiment of the preparation method described above in this invention, in step S1, the drying temperature is 50-80°C.

[0046] As a specific embodiment of the preparation method described above in this invention, in S1, the film-forming mold needs to be calibrated with a level beforehand.

[0047] In one specific embodiment of the preparation method described above in this invention, in step S1, the obtained mixed solution (i.e., casting solution) is evenly and smoothly spread in the film-forming apparatus, and then a glass plate is covered on the film-forming apparatus to prevent chloroform from evaporating too quickly.

[0048] In one specific embodiment of the preparation method described above in this invention, in step S2, the calcination is carried out at 450-470°C for 0.2-3 hours.

[0049] As a specific embodiment of the preparation method described above in this invention, in step S2, the calcination is carried out at 450-470°C for 0.2-1 hours.

[0050] In a specific embodiment of the preparation method described above in this invention, in step S2, the inert atmosphere includes an argon atmosphere.

[0051] As a specific embodiment of the preparation method described above in this invention, in S2, after calcination, the temperature of the obtained product is reduced to room temperature - 30°C to obtain the mixed matrix membrane containing a high loading of ZIF-62.

[0052] As a specific embodiment of the preparation method described above in this invention, in S2, the calcination process employs programmed temperature rise, which includes:

[0053] The film-forming material dried in S1 is heated from room temperature -30℃ to 450-470℃ for 200-350 min and maintained for 0.2-3 h, and then cooled to room temperature -30℃ for 300-450 min.

[0054] On the other hand, the present invention also provides a mixed matrix membrane containing a high loading of ZIF-62 prepared by the above-described method for preparing a mixed matrix membrane containing a high loading of ZIF-62.

[0055] As a specific embodiment of the hybrid matrix membrane described above in this invention, the hybrid matrix membrane containing a high loading of ZIF-62 has a ZIF-62 doping amount of 0-80 wt%, preferably 5-80 wt%.

[0056] Compared with methods for surface modification of porous or polymeric materials, the melt preparation method provided by this invention has lower costs, simpler operation, reduces the use of organic reagents, lowers environmental pollution, and is easier to scale up. Furthermore, this preparation method can yield defect-free composite membranes with filler loadings up to 80 wt%, which can be used as high-performance gas separation membranes.

[0057] In another aspect, the present invention also provides the application of the above-described hybrid matrix membrane containing a high loading of ZIF-62 in gas separation.

[0058] As a specific embodiment of the application described above in this invention, the gas separation includes the separation of propane and propylene.

[0059] As a specific embodiment of the application described above in this invention, in the separation process of propane and propylene, a single-component gas permeation test is conducted using the Wicke-Kallenbach permeation technique, wherein argon is used as the purge gas, the argon flow rate is 100 mL / min, and the test temperature is 25 °C.

[0060] Compared with the prior art, the beneficial technical effects achieved by the present invention include:

[0061] This invention utilizes ZIF-62, a glassy MOF material with melting properties, as a filler to prepare high-load MMMs through a melting process. This melting process avoids the generation of non-selective voids in the MMMs as the filler loading increases. Simultaneously, it avoids the additional complex modification or synthesis processes required for preparing defect-free, high-load mixed matrix membranes. The high-temperature treated tg-ZIF-62 / PIM-1 MMMs prepared by this invention are defect-free composite membrane materials with a ZIF-62 filler loading as high as 80 wt%. Compared to untreated ZIF-62 / PIM-1 mixed matrix membranes (ZIF-62 / PIM-1 MMMs), i.e., precursor mixed matrix membrane materials, the tg-ZIF-62 / PIM-1 MMMs exhibit a higher propane / propylene separation ratio, indicating its suitability for separating propane and propylene mixed gases. Attached Figure Description

[0062] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0063] Figure 1 The XRD patterns of the ZIF-62 powder products obtained in Examples 1-4 and Comparative Example 1 of this invention are shown in Test Example 1.

[0064] Figure 2a The image shown is a front scanning electron microscope (SEM) image of the precursor membrane material, ZIF-62 / PIM-1MMMs (78 wt% ZIF-62), prepared in Example 1 of Test Example 2 of this invention.

[0065] Figure 2b This is a front scanning electron microscope image of the precursor membrane material ZIF-62 / PIM-1MMMs (52wt% ZIF-62) prepared in Example 4 of Test Example 2 of the present invention.

[0066] Figure 3a This is a front scanning electron microscope image of M1 obtained in Example 1 of Test Example 2 of the present invention.

[0067] Figure 3b This is a front scanning electron microscope image of M4 obtained in Example 4 of Test Example 2 of the present invention. Detailed Implementation

[0068] It should be noted that the term "comprising" and any variations thereof in the specification, claims, and accompanying drawings of this invention are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or device that includes a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or devices.

[0069] The "range" disclosed in this invention is given in the form of a lower limit and an upper limit. It can be one or more lower limits and one or more upper limits, respectively. A given range is defined by selecting a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges defined in this way are composable, meaning that any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for specific parameters, it is also expected that ranges of 60-110 and 80-120 are also expected. Furthermore, if the listed minimum range values ​​are 1 and 2, and the listed maximum range values ​​are 3, 4, and 5, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5.

[0070] In this invention, unless otherwise specified, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this invention, and "0-5" is simply a shortened representation of these numerical combinations.

[0071] In this invention, unless otherwise specified, all embodiments and preferred embodiments mentioned in this invention can be combined with each other to form new technical solutions.

[0072] In this invention, unless otherwise specified, all technical features and preferred features mentioned in this invention can be combined with each other to form new technical solutions.

[0073] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying tables, drawings, and embodiments. The embodiments described below are some, but not all, embodiments of this invention, and are only used to illustrate the invention, and should not be considered as limiting the scope of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0074] Example 1

[0075] This embodiment provides a hybrid matrix membrane containing a high-loading glassy MOF ZIF-62, which is prepared by a method including the following specific steps:

[0076] (1) Preparation of the inherently microporous polymer PIM-1:

[0077] 1) Recrystallization of 5,5',6,6'-tetrahydroxy-3,3',3,3'-tetramethyl-1,1'-spirobisindane (TTSBI):

[0078] 10g of TTSBI to be purified was dissolved in 80g of hot methanol. The solvent was further evaporated by heating, removing approximately 40g. Dichloromethane was then slowly added dropwise until turbidity was formed. After standing for about 2 hours, a white solid was obtained by vacuum filtration. The obtained white solid was further dried in a vacuum drying oven at 60°C for two days until the product quality no longer decreased, yielding purified TTSBI.

[0079] 2) Purification of tetrafluoroterephthalonitrile (TFTPN):

[0080] Take an appropriate amount of TFTPN to be purified in a sublimator, control the system temperature at 145℃, and maintain the sublimation process under vacuum conditions, such as a pressure of -0.02MPa, to obtain purified TFTPN.

[0081] 3) Polymerization reaction process:

[0082] 1.0 g (5 mmol) of purified TFTPN, 1.70 g (5 mmol) of purified TTSBI and 2.07 g (15 mmol) of anhydrous K2CO3 were mixed and 20 mL of anhydrous DMF was added under a nitrogen atmosphere. The mixture was stirred until the reactants were completely dissolved. The temperature was then raised to 65 °C and the reaction was maintained under a nitrogen atmosphere for 72 hours. After the reaction was completed, a viscous yellow solution was obtained.

[0083] 4) Post-processing:

[0084] After the reaction solution cooled, it was slowly poured into 150 mL of methanol. Vacuum filtration was performed to obtain a bright yellow product. This product was dissolved in dichloromethane, and after filtration, the filtrate was precipitated again in methanol. Vacuum filtration was then performed to obtain a solid product. This process was repeated three times. The obtained solid was washed and filtered with ultrapure water, and finally dried in a vacuum drying oven at 80 °C for 12-24 h to obtain a bright yellow solid product, namely the intrinsically microporous polymer PIM-1.

[0085] (2) Preparation of ZIF-62:

[0086] 1.515 g Zn(NO3)2·6H2O, 7.35 g imidazole, 1.418 g benzimidazole, and 75 mL DMF were mixed, stirred to dissolve, and stirred continuously at room temperature for 12 hours. The product was collected by centrifugation and washed three times with DMF / EtOH to remove unreacted reactants, yielding ZIF-62.

[0087] (3) Preparation of ZIF-62 / PIM-1MMMs:

[0088] Accurately weigh 312 mg of the ZIF-62 sample obtained in step (2) and disperse it in 10 mL of chloroform by stirring and sonicating for 10 minutes each. Add 88 mg of the PIM-1 sample obtained in step (1) in three portions according to 1 / 10, 2 / 10 and 7 / 10 of the total mass to the chloroform suspension of ZIF-62 obtained in the previous step, and repeat the stirring and sonicating for 10 minutes each time to ensure thorough dispersion. Sonicate the final mixed solution again for 10 minutes, and then slowly spread it into a film-forming mold calibrated with a level. Cover the film-forming mold with a glass plate to prevent the chloroform from evaporating too quickly to obtain a relatively uniform mixed matrix film. Then place it at 25°C for evaporation for 12 hours. The initially obtained membrane material is vacuum dried at 80°C overnight to remove excess solvent, resulting in a ZIF-62 / PIM-1 mixed matrix film doped with 78 wt% ZIF-62, denoted as ZIF-62 / PIM-1MMMs (78 wt% ZIF-62).

[0089] (4) Preparation of tg-ZIF-62 / PIM-1MMMs:

[0090] The ZIF-62 / PIM-1 mixed matrix film prepared in step (3) was subjected to programmed temperature rise melting and quenching under an argon atmosphere. The initial temperature of the sample was 30°C, and the temperature was raised to 470°C over a period of 300 minutes and maintained for 180 minutes. Then, the temperature was lowered to 30°C over a period of 400 minutes to obtain a mixed matrix film containing a high loading of glassy MOF ZIF-62, denoted as M1, in which the ZIF-62 doping content was 78 wt%.

[0091] Example 2

[0092] This embodiment provides a hybrid matrix membrane containing a high-loading glassy MOF ZIF-62, which is prepared by a method including the following specific steps:

[0093] (1) Preparation of PIM-1, an intrinsically microporous polymer

[0094] 1) Recrystallization of 5,5',6,6'-tetrahydroxy-3,3',3,3'-tetramethyl-1,1'-spirobisindane (TTSBI):

[0095] 10g of TTSBI to be purified was dissolved in 80g of hot methanol. The solvent was further evaporated by heating, removing approximately 40g. Dichloromethane was then slowly added dropwise until turbidity was formed. After standing for about 2 hours, a white solid was obtained by vacuum filtration. The obtained white solid was further dried in a vacuum drying oven at 60°C for two days until the product quality no longer decreased, yielding purified TTSBI.

[0096] 2) Purification of tetrafluoroterephthalonitrile (TFTPN):

[0097] Take an appropriate amount of TFTPN to be purified in a sublimator, control the system temperature at 145℃, and maintain the sublimation process under vacuum conditions, such as a pressure of -0.02MPa, to obtain purified TFTPN.

[0098] 3) Polymerization reaction process:

[0099] 1.0 g (5 mmol) of purified TFTPN, 1.70 g (5 mmol) of purified TTSBI and 2.07 g (15 mmol) of anhydrous K2CO3 were mixed and 20 mL of anhydrous DMF was added under a nitrogen atmosphere. The mixture was stirred until the reactants were completely dissolved. The temperature was then raised to 65 °C and the reaction was maintained under a nitrogen atmosphere for 72 hours. After the reaction was completed, a viscous yellow solution was obtained.

[0100] 4) Post-processing:

[0101] After the reaction solution cooled, it was slowly poured into 150 mL of methanol. Vacuum filtration was performed to obtain a bright yellow product. This product was dissolved in dichloromethane, and after filtration, the filtrate was precipitated again in methanol. Vacuum filtration was then performed to obtain a solid product. This process was repeated three times. The obtained solid was washed and filtered with ultrapure water, and finally dried in a vacuum drying oven at 80 °C for 12-24 h to obtain a bright yellow solid product, namely the intrinsically microporous polymer PIM-1.

[0102] (2) Preparation of ZIF-62:

[0103] 1.515 g Zn(NO3)2·6H2O, 7.35 g imidazole, 1.418 g benzimidazole, and 75 mL DMF were mixed, stirred to dissolve, and stirred continuously at room temperature for 12 hours. The product was collected by centrifugation and washed three times with DMF / EtOH to remove unreacted reactants, yielding ZIF-62.

[0104] (3) Preparation of ZIF-62 / PIM-1MMMs:

[0105] Accurately weigh 312 mg of the ZIF-62 sample obtained in step (2) and disperse it in 10 mL of chloroform by stirring and sonicating for 10 minutes each. Add 88 mg of the PIM-1 sample obtained in step (1) to the chloroform suspension of ZIF-62 obtained in the previous step in three portions according to 1 / 10, 2 / 10 and 7 / 10 of the total mass, and repeat the stirring and sonicating for 10 minutes each time to ensure thorough dispersion. Sonicate the final mixed solution again for 10 minutes, and then slowly spread it evenly in a film-forming mold calibrated with a level. Cover the film-forming mold with a glass plate to prevent the chloroform from evaporating too quickly to obtain a relatively uniform mixed matrix film. Then place it at a temperature of 10°C for evaporation for 12 hours. The initially obtained membrane material is vacuum dried at 80°C overnight to remove excess solvent, resulting in a ZIF-62 / PIM-1 mixed matrix film doped with 78 wt% ZIF-62, denoted as ZIF-62 / PIM-1MMMs (78 wt% ZIF-62).

[0106] (4) Preparation of tg-ZIF-62 / PIM-1MMMs:

[0107] The ZIF-62 / PIM-1 mixed matrix film prepared in step (3) was subjected to programmed temperature rise melting and quenching under an argon atmosphere. The initial temperature of the sample was 30°C, and the temperature was increased to 470°C over a period of 300 minutes and maintained for 180 minutes. Then, the temperature was cooled to 30°C over a period of 400 minutes to obtain a mixed matrix film containing a high loading of glassy MOF ZIF-62, denoted as M2, in which the ZIF-62 doping content was 78 wt%.

[0108] Example 3

[0109] This embodiment provides a hybrid matrix membrane containing a high-loading glassy MOF ZIF-62, which is prepared by a method including the following specific steps:

[0110] (1) Preparation of PIM-1, an intrinsically microporous polymer

[0111] 1) Recrystallization of 5,5',6,6'-tetrahydroxy-3,3',3,3'-tetramethyl-1,1'-spirobisindane (TTSBI):

[0112] 10g of TTSBI to be purified was dissolved in 80g of hot methanol. The solvent was further evaporated by heating, removing approximately 40g. Dichloromethane was then slowly added dropwise until turbidity was formed. After standing for about 2 hours, a white solid was obtained by vacuum filtration. The obtained white solid was further dried in a vacuum drying oven at 60°C for two days until the product quality no longer decreased, yielding purified TTSBI.

[0113] 2) Purification of tetrafluoroterephthalonitrile (TFTPN):

[0114] Take an appropriate amount of TFTPN to be purified in a sublimator, control the system temperature at 145℃, and maintain the sublimation process under vacuum conditions, such as a pressure of -0.02MPa, to obtain purified TFTPN.

[0115] 3) Polymerization reaction process:

[0116] 1.0 g (5 mmol) of purified TFTPN, 1.70 g (5 mmol) of purified TTSBI and 2.07 g (15 mmol) of anhydrous K2CO3 were mixed and 20 mL of anhydrous DMF was added under a nitrogen atmosphere. The mixture was stirred until the reactants were completely dissolved. The temperature was then raised to 65 °C and the reaction was maintained under a nitrogen atmosphere for 72 hours. After the reaction was completed, a viscous yellow solution was obtained.

[0117] 4) Post-processing:

[0118] After the reaction solution cooled, it was slowly poured into 150 mL of methanol. Vacuum filtration was performed to obtain a bright yellow product. This product was dissolved in dichloromethane, and after filtration, the filtrate was precipitated again in methanol. Vacuum filtration was then performed to obtain a solid product. This process was repeated three times. The obtained solid was washed and filtered with ultrapure water, and finally dried in a vacuum drying oven at 80 °C for 12-24 h to obtain a bright yellow solid product, namely the intrinsically microporous polymer PIM-1.

[0119] (2) Preparation of ZIF-62:

[0120] 1.515 g Zn(NO3)2·6H2O, 7.35 g imidazole, 1.418 g benzimidazole, and 75 mL DMF were mixed, stirred to dissolve, and stirred continuously at room temperature for 12 hours. The product was collected by centrifugation and washed three times with DMF / EtOH to remove unreacted reactants, yielding ZIF-62.

[0121] (3) Preparation of ZIF-62 / PIM-1MMMs:

[0122] Accurately weigh 312 mg of the ZIF-62 sample obtained in step (2) and disperse it in 10 mL of chloroform by stirring and sonicating for 10 minutes each. Add 88 mg of the PIM-1 sample obtained in step (1) in three portions according to 1 / 10, 2 / 10 and 7 / 10 of the total mass to the chloroform suspension of ZIF-62 obtained in the previous step, and repeat the stirring and sonicating for 10 minutes each time to ensure thorough dispersion. Sonicate the final mixed solution again for 10 minutes, and then slowly spread it into a film-forming mold calibrated with a level. Cover the film-forming mold with a glass plate to prevent the chloroform from evaporating too quickly to obtain a relatively uniform mixed matrix film. Then place it at 25°C for evaporation for 12 hours. The initially obtained membrane material is vacuum dried at 80°C overnight to remove excess solvent, resulting in a ZIF-62 / PIM-1 mixed matrix film doped with 78 wt% ZIF-62, denoted as ZIF-62 / PIM-1MMMs (78 wt% ZIF-62).

[0123] (4) Preparation of tg-ZIF-62 / PIM-1MMMs:

[0124] The ZIF-62 / PIM-1 mixed matrix film prepared in step (3) was subjected to programmed temperature rise melting and quenching under an argon atmosphere. The initial temperature of the sample was 30°C, and the temperature was increased to 450°C over a period of 300 minutes and maintained for 180 minutes. Then, the temperature was cooled to 30°C over a period of 400 minutes to obtain a mixed matrix film containing a high loading of glassy MOF ZIF-62, denoted as M3, in which the ZIF-62 doping content was 78 wt%.

[0125] The lower the amount of porous filler added, the closer the performance of the prepared MMMs is to the performance of the polymer itself. Therefore, preparing MMMs with a high proportion of porous filler doping and no interfacial defects is of great significance for improving separation performance.

[0126] Example 4

[0127] This embodiment provides a hybrid matrix membrane containing a high-loading glassy MOF ZIF-62, which is prepared by a method including the following specific steps:

[0128] (1) Preparation of the inherently microporous polymer PIM-1:

[0129] 1) Recrystallization of 5,5',6,6'-tetrahydroxy-3,3',3,3'-tetramethyl-1,1'-spirobisindane (TTSBI):

[0130] 10g of TTSBI to be purified was dissolved in 80g of hot methanol. The solvent was further evaporated by heating, removing approximately 40g. Dichloromethane was then slowly added dropwise until turbidity was formed. After standing for about 2 hours, a white solid was obtained by vacuum filtration. The obtained white solid was further dried in a vacuum drying oven at 60°C for two days until the product quality no longer decreased, yielding purified TTSBI.

[0131] 2) Purification of tetrafluoroterephthalonitrile (TFTPN):

[0132] Take an appropriate amount of TFTPN to be purified in a sublimator, control the system temperature at 145℃, and maintain the sublimation process under vacuum conditions, such as a pressure of -0.02MPa, to obtain purified TFTPN.

[0133] 3) Polymerization reaction process:

[0134] 1.0 g (5 mmol) of purified TFTPN, 1.70 g (5 mmol) of purified TTSBI and 2.07 g (15 mmol) of anhydrous K2CO3 were mixed and 20 mL of anhydrous DMF was added under a nitrogen atmosphere. The mixture was stirred until the reactants were completely dissolved. The temperature was then raised to 65 °C and the reaction was maintained under a nitrogen atmosphere for 72 hours. After the reaction was completed, a viscous yellow solution was obtained.

[0135] 4) Post-processing:

[0136] After the reaction solution cooled, it was slowly poured into 150 mL of methanol. Vacuum filtration was performed to obtain a bright yellow product. This product was dissolved in dichloromethane, and after filtration, the filtrate was precipitated again in methanol. Vacuum filtration was then performed to obtain a solid product. This process was repeated three times. The obtained solid was washed and filtered with ultrapure water, and finally dried in a vacuum drying oven at 80 °C for 12-24 h to obtain a bright yellow solid product, namely the intrinsically microporous polymer PIM-1.

[0137] (2) Preparation of ZIF-62:

[0138] 1.515 g Zn(NO3)2·6H2O, 7.35 g imidazole, 1.418 g benzimidazole, and 75 mL DMF were mixed, stirred to dissolve, and stirred continuously at room temperature for 12 hours. The product was collected by centrifugation and washed three times with DMF / EtOH to remove unreacted reactants, yielding ZIF-62.

[0139] (3) Preparation of ZIF-62 / PIM-1MMMs:

[0140] Accurately weigh 208 mg of the ZIF-62 sample obtained in step (2) and disperse it in 10 mL of chloroform by stirring and sonicating for 10 minutes each. Add 192 mg of the PIM-1 sample obtained in step (1) to the chloroform suspension of ZIF-62 obtained in the previous step in three portions according to 1 / 10, 2 / 10 and 7 / 10 of the total mass, and repeat the stirring and sonicating for 10 minutes each time to ensure thorough dispersion. The resulting mixed solution was sonicated again for 10 minutes, and then slowly spread into a film-forming mold calibrated with a level. A glass plate was placed over the film-forming mold to prevent chloroform from evaporating too quickly to obtain a more uniform mixed matrix film. The film was then evaporated at 25°C for 12 hours. The initially obtained membrane material was vacuum dried overnight at 80°C to remove excess solvent, resulting in a ZIF-62 / PIM-1 mixed matrix film doped with 52wt% ZIF-62, denoted as ZIF-62 / PIM-1MMMs (52wt% ZIF-62).

[0141] (4) Preparation of tg-ZIF-62 / PIM-1MMMs:

[0142] The ZIF-62 / PIM-1 mixed matrix film prepared in step (3) was subjected to programmed temperature rise melting and quenching under an argon atmosphere. The initial temperature of the sample was 30°C, and the temperature was increased to 470°C over a period of 300 minutes and maintained for 180 minutes. Then, the temperature was cooled to 30°C over a period of 400 minutes to obtain a mixed matrix film containing a high loading of glassy MOF ZIF-62, denoted as M4, in which the ZIF-62 doping content was 52 wt%.

[0143] Comparative Example 1

[0144] This comparative example provides a hybrid matrix membrane containing a high-loading glassy MOF ZIF-62, which is prepared by a method including the following specific steps:

[0145] (1) Preparation of the inherently microporous polymer PIM-1:

[0146] 1) Recrystallization of 5,5',6,6'-tetrahydroxy-3,3',3,3'-tetramethyl-1,1'-spirobisindane (TTSBI):

[0147] 10g of TTSBI to be purified was dissolved in 80g of hot methanol. The solvent was further evaporated by heating, removing approximately 40g. Dichloromethane was then slowly added dropwise until turbidity was formed. After standing for about 2 hours, a white solid was obtained by vacuum filtration. The obtained white solid was further dried in a vacuum drying oven at 60°C for two days until the product quality no longer decreased, yielding purified TTSBI.

[0148] 2) Purification of tetrafluoroterephthalonitrile (TFTPN):

[0149] Take an appropriate amount of TFTPN to be purified in a sublimator, control the system temperature at 145℃, and maintain the sublimation process under vacuum conditions, such as a pressure of -0.02MPa, to obtain purified TFTPN.

[0150] 3) Polymerization reaction process:

[0151] 1.0 g (5 mmol) of purified TFTPN, 1.70 g (5 mmol) of purified TTSBI and 2.07 g (15 mmol) of anhydrous K2CO3 were mixed and 20 mL of anhydrous DMF was added under a nitrogen atmosphere. The mixture was stirred until the reactants were completely dissolved. The temperature was then raised to 65 °C and the reaction was maintained under a nitrogen atmosphere for 72 hours. After the reaction was completed, a viscous yellow solution was obtained.

[0152] 4) Post-processing:

[0153] After the reaction solution cooled, it was slowly poured into 150 mL of methanol. Vacuum filtration was performed to obtain a bright yellow product. This product was dissolved in dichloromethane, and after filtration, the filtrate was precipitated again in methanol. Vacuum filtration was then performed to obtain a solid product. This process was repeated three times. The obtained solid was washed and filtered with ultrapure water, and finally dried in a vacuum drying oven at 80 °C for 12-24 h to obtain a bright yellow solid product, namely the intrinsically microporous polymer PIM-1.

[0154] (2) Preparation of ZIF-62:

[0155] 1.515 g Zn(NO3)2·6H2O, 7.35 g imidazole, 1.418 g benzimidazole, and 75 mL DMF were mixed, stirred to dissolve, and stirred continuously at room temperature for 12 hours. The product was collected by centrifugation and washed three times with DMF / EtOH to remove unreacted reactants, yielding ZIF-62.

[0156] (3) Preparation of ZIF-62 / PIM-1MMMs:

[0157] Accurately weigh 312 mg of the ZIF-62 sample obtained in step (2) and disperse it in 10 mL of chloroform by stirring and sonicating for 10 minutes each. Add 88 mg of the PIM-1 sample obtained in step (1) in three portions according to 1 / 10, 2 / 10 and 7 / 10 of the total mass to the chloroform suspension of ZIF-62 obtained in the previous step, and repeat the stirring and sonicating for 10 minutes each time to ensure thorough dispersion. Sonicate the final mixed solution again for 10 minutes, and then slowly spread it evenly in a film-forming mold calibrated with a level. Cover the film-forming mold with a glass plate to prevent the chloroform from evaporating too quickly to obtain a relatively uniform mixed matrix film. Then place it at 25°C for evaporation for 12 hours. The initially obtained membrane material is vacuum dried at 80°C overnight to remove excess solvent, resulting in a ZIF-62 / PIM-1 mixed matrix film doped with 78 wt% ZIF-62, denoted as M5.

[0158] The composition and preparation conditions of membranes M1-M4 prepared in Examples 1-4 of the present invention and membrane M5 prepared in Comparative Example 1 are shown in Table 1 below.

[0159] Table 1

[0160]

[0161] The incorporation ratio of porous fillers has a significant impact on MMMs. Therefore, to compare the differences in propane / propylene gas separation performance of mixed matrix membranes with different ZIF-62 loadings, Table 1 above shows that membranes with different ZIF-62 loadings were prepared in the embodiments of the present invention, including MMMs with ZIF-62 loadings of 78 wt% and 52 wt%.

[0162] Test Example 1

[0163] In this test example, the ZIF-62 powder products obtained in Examples 1-4 and Comparative Example 1 were characterized by X-ray electron diffraction (XRD) using a LabX XRD-6000 X-ray diffractometer manufactured by Shimadzu Corporation, Japan. The test procedure used a Cu emission field, and the 2θ range was 5-50°. The obtained XRD patterns are shown below. Figure 1 As shown. For example Figure 1 As shown in the simulated (ZIF-62 powder standard material) XRD diffraction pattern, ZIF-62 structured powder products were successfully obtained in Examples 1-4 and Comparative Example 1 by room temperature synthesis method.

[0164] Test Example 2

[0165] In this test example, a JEOL JSM-6510A analytical scanning electron microscope was used to characterize the morphology of the precursor membrane samples prepared in Examples 1 and 4, namely ZIF-62 / PIM-1MMMs (78 wt% ZIF-62), ZIF-62 / PIM-1MMMs (52 wt% ZIF-62), and the finished membrane samples (M1 and M4). The SEM images of the precursor membrane samples are shown below. Figures 2a-2b As shown, the SEM image of the finished membrane sample is as follows. Figures 3a-3b As shown.

[0166] from Figures 2a-2b It can be clearly seen that there are obvious protrusions on the surface of ZIF-62 / PIM-1MMMs (78wt% ZIF-62) and ZIF-62 / PIM-1MMMs (52wt% ZIF-62) precursor membrane materials, and obvious defects can be observed on the surface of ZIF-62 / PIM-1MMMs (52wt% ZIF-62) precursor membrane material. This indicates that if the process is not carried out by melting, there will be void defects between the porous filler and the polymer in the MMMs that affect selectivity.

[0167] from Figures 3a-3b It can be clearly seen that, compared with the precursor membrane material without high-temperature treatment, the surfaces of M1 and M4 are flatter and without obvious defects, indicating that ZIF-62 melted during the high-temperature treatment process in the preparation of the membrane material and compensated for the aforementioned void defects.

[0168] Test Example 3

[0169] This test case investigated the separation performance of propane / propylene by Examples 1-4 and Comparative Examples M1-M5. The gas separation test used a Wicke-Kallenbach Technique apparatus (see Angew. Chem. Int. Ed. 2006, 45, 7053-7056). The flow rates of propane / propylene and carrier gas Ar were controlled by a mass flow controller, with an argon flow rate of 100 mL / min and a test temperature of 25°C. The feed gas permeating the membrane was purged by the carrier gas into the gas chromatograph, and the content of different gases was measured to ultimately determine the separation effect. The gas chromatography (GC) analysis conditions were: Shimadzu GC2014, column temperature 50°C, TCD detector, and the mixed gas composition was propane and propylene in a 1:1 volume ratio.

[0170] Additionally, in this test example, before testing the gas permeability coefficient of M1-M5, the membranes need to be soaked in methanol overnight and then vacuum dried at 80°C.

[0171] The propane / propylene separation performance test results of membranes M1-M5 obtained in this test example are shown in Table 2 below.

[0172] Table 2. Gas flux of M1-M5 to propane / propylene and ideal separation factor at 25℃.

[0173]

[0174] Note: In Table 2, flux is the volume of gas that permeates per unit membrane area per unit time.

[0175] GPU: 1×10 -6 cm 3 cm -2 s -1 cmHg -1 .

[0176] As can be seen from Table 2 above, with the increase of ZIF-62 loading, the separation ratio of propane / propylene gas by the tg-ZIF-62 / PIM-1 mixed matrix membrane prepared in the embodiments of the present invention is also correspondingly improved, further proving that increasing the loading of the packing material has an important impact on improving the performance of the mixed matrix membrane. In addition, the relevant experimental data of M1-M3 and M5 shown in Table 2 also show that, compared with the M5 membrane prepared without high-temperature melting treatment in Comparative Example 1, although the C3H6 flux and C3H8 flux of the M1-M3 membrane prepared after high-temperature melting treatment in the embodiments of the present invention are reduced, they have a higher propane / propylene separation ratio, thus indicating that these membranes are more suitable for the separation of propane and propylene mixed gases.

[0177] The above description is merely a specific embodiment of the present invention and should not be construed as limiting the scope of the invention. Therefore, any substitution of equivalent components or equivalent changes and modifications made within the scope of protection of this patent should still fall within the scope of this patent. Furthermore, the technical features, technical features and technical inventions, and technical inventions in this invention can be freely combined and used.

Claims

1. A method for preparing a hybrid matrix membrane containing a high loading of ZIF-62, characterized in that, include: S1: The inherently microporous polymer PIM-1 and ZIF-62 are dispersed in chloroform, and the resulting mixed solution is evenly and evenly spread in a film-forming device, followed by natural evaporation, and then the resulting film material is dried; wherein, the mass ratio of ZIF-62 to the inherently microporous polymer PIM-1 is 52:48-78:22, and the temperature of natural evaporation is 10-25℃; S2: The film-forming material after drying in S1 is calcined in an inert atmosphere to obtain the mixed matrix film containing high loading of ZIF-62 after calcination, wherein the calcination temperature is 450-470℃.

2. The preparation method according to claim 1, characterized in that, In S1, the inherently microporous polymers PIM-1 and ZIF-62 are dispersed in chloroform, including: S11: Dissolve ZIF-62 in chloroform and disperse it evenly; S12: Dissolve the inherently microporous polymer PIM-1 in the dispersion obtained in S11 and disperse it uniformly to form a homogeneous mixed solution; or; 1): Dissolve the inherently microporous polymer PIM-1 in chloroform and disperse it uniformly to form solution A; 2): Dissolve ZIF-62 in chloroform and disperse it evenly to form solution B; 3): Mix solution A and solution B thoroughly to form a homogeneous mixed solution.

3. The preparation method according to claim 2, characterized in that, In S12, the inherently microporous polymer PIM-1 is dissolved in batches in the dispersion obtained in S11 and then uniformly dispersed.

4. The preparation method according to claim 3, characterized in that, The batching is divided into 3 batches.

5. The preparation method according to claim 4, characterized in that, When the inherently microporous polymer PIM-1 was dissolved in the dispersion obtained by dissolving it in S11 in 3 batches, the mass ratio of the inherently microporous polymer PIM-1 added in each batch was 1:2:

7.

6. The preparation method according to claim 2, characterized in that, In step 3), the process of thoroughly mixing liquid A and liquid B involves mixing liquid B with liquid A in batches.

7. The preparation method according to claim 6, characterized in that, The batching is divided into 3 batches.

8. The preparation method according to claim 7, characterized in that, When mixing solution B with solution A in 3 batches, the mass ratio of ZIF-62 added in each batch should be controlled to be 1:2:

7.

9. The preparation method according to claim 1 or 2, characterized in that, In S1, the preparation method of the inherently microporous polymer PIM-1 includes: TFTPN, TTSBI, anhydrous K2CO3 and anhydrous N,N-dimethylformamide were stirred and refluxed under a nitrogen atmosphere to obtain a reaction solution. After the reaction solution was cooled, it was slowly poured into methanol and filtered under vacuum to obtain a bright yellow solid. The obtained bright yellow solid was dissolved in dichloromethane, filtered, and the filtrate was precipitated again in methanol. The solid product was obtained by vacuum filtration. This step was repeated. The obtained solid was then washed and filtered, and finally dried in a vacuum drying oven to obtain a bright yellow product, which is the inherently microporous polymer PIM-1.

10. The preparation method according to claim 9, characterized in that, In S1, the preparation method of the inherently microporous polymer PIM-1 specifically includes: 1) Recrystallization of 5,5',6,6'-tetrahydroxy-3,3',3,3'-tetramethyl-1,1'-spirobisindane, i.e., TTSBI: Dissolve the TTSBI to be purified in an appropriate amount of hot methanol, and further heat to evaporate half of the solvent. Then slowly add dichloromethane dropwise to the solution until turbidity is produced. Let it stand for 2-3 hours, and obtain a white solid by vacuum filtration. Then dry the obtained white solid in a vacuum drying oven at 50-70℃ until the product quality no longer decreases, and obtain purified TTSBI. 2) Purification of tetrafluoroterephthalonitrile, i.e., TFTPN: Take an appropriate amount of TFTPN to be purified in a micro-sublimation apparatus, and sublimate the system under vacuum conditions at a temperature of 140-150℃ to obtain purified TFTPN. 3) Polymerization reaction: Purified TFTPN, purified TTSBI, and anhydrous K2CO3 in a molar ratio of 1-1.5:1-1.5:3-4.5 were added to a reactor. An appropriate amount of anhydrous N,N-dimethylformamide was added under a nitrogen atmosphere. The mixture was stirred until the reactants were completely dissolved. The temperature was then raised to 40-80℃ and the reaction was maintained under a nitrogen atmosphere for 40-80 hours. After the reaction was completed, a viscous yellow solution was obtained. 4) Post-processing: After the reaction solution cools, slowly pour it into an appropriate amount of methanol. Obtain a bright yellow solid by vacuum filtration. Dissolve the obtained solid in dichloromethane, filter it, and then precipitate the filtrate again in methanol. Obtain the solid product by vacuum filtration. Repeat the above operation. Then wash and filter the obtained solid with ultrapure water. Finally, dry it in a vacuum drying oven at 70-80℃ for 12-24 hours to obtain a bright yellow product, which is the inherently microporous polymer PIM-1.

11. The preparation method according to claim 1 or 2, characterized in that, In S1, the preparation method of ZIF-62 includes: A mixture of Zn(NO3)2·6H2O, imidazole, benzimidazole, and an appropriate amount of DMF in a mass ratio of 1-1.5:4.5-6:1-1.5 was stirred continuously at 25-100℃ for 10-14 hours. The product was then collected by centrifugation and washed to remove unreacted reactants.

12. The preparation method according to claim 11, characterized in that, The product was washed three times each with DMF and EtOH to remove unreacted reactants.

13. The preparation method according to claim 1 or 2, characterized in that, In S1, the natural evaporation time is 10-14 hours.

14. The preparation method according to claim 1 or 2, characterized in that, In S1, the drying temperature is 50-80℃.

15. The preparation method according to claim 1, characterized in that, In S2, the roasting time is 0.2-3 hours.

16. The preparation method according to claim 15, characterized in that, In S2, the inert atmosphere includes an argon atmosphere.

17. The preparation method according to claim 15, characterized in that, In S2, after calcination, the temperature of the resulting product is lowered to room temperature - 30°C to obtain the mixed matrix membrane containing a high loading of ZIF-62.

18. The preparation method according to any one of claims 1, 15-17, characterized in that, In S2, the roasting process employs programmed temperature increase, which includes: The film-forming material dried in S1 is heated from room temperature -30℃ to 450-470℃ for 200-350 min and maintained for 0.2-3 h, and then cooled to room temperature -30℃ for 300-450 min.

19. A mixed matrix membrane containing a high loading of ZIF-62, prepared by the method for preparing a mixed matrix membrane containing a high loading of ZIF-62 according to any one of claims 1-18, characterized in that, In the mixed matrix film containing a high loading of ZIF-62, the doping amount of ZIF-62 is 52-78 wt%.

20. The application of the hybrid matrix membrane containing a high loading of ZIF-62 as described in claim 19 in gas separation.

21. The application according to claim 20, characterized in that, The gas separation includes the separation of propane and propylene.

22. The application according to claim 21, characterized in that, In the separation process of propane and propylene, a single-component gas permeation test was conducted using the Wicke-Kallenbach permeation technique, with argon as the purge gas, an argon flow rate of 100 mL / min, and a test temperature of 25 °C.

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