Polyimide gas separation membranes and methods comprising binary amines containing carbazolyl motifs and preparation thereof

Abstract

The application relates to a polyimide gas separation membrane containing a carbazole group and a preparation method thereof, and belongs to the technical field of gas separation and purification. The preparation method of the polyimide gas separation membrane is as follows: firstly, a kind of binary amine functional molecule containing a carbazole group is synthesized; then, C-N coupling reaction is carried out on the binary amine functional molecule and nitrohalobenzene to obtain an aromatic bis-nitro compound containing a hydrogen bond active site (-NH-); finally, hydrogen reduction is carried out to obtain a target molecule, FNPA diamine. After polycondensation of the FNPA diamine and a binary acid anhydride, a polyamide acid precursor is obtained; after cyclization and dehydration, a polyimide is obtained; finally, a polyimide gas separation membrane containing a carbazole group and synergistic hydrogen bond interaction is obtained through a dissolving-tape casting method. The application significantly improves the reaction yield of the FNPA monomer, shortens the preparation period of the monomer, simplifies the post-treatment process, and simultaneously has excellent thermal performance, mechanical performance and gas separation performance of the polyimide gas separation membrane material.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of gas separation and purification, and particularly relates to a binary amine containing a carbazole unit and a polyimide gas separation membrane and method for preparing the same. BACKGROUND

[0002] Membrane separation is a new green gas purification technology, which has the advantages of continuous high efficiency, small equipment footprint, simple operation, environmental friendliness, etc. compared with traditional cryogenic separation, pressure swing adsorption separation, etc. It can realize efficient separation under mild conditions and has been successfully applied to natural gas biogas upgrading, helium purification, in-situ nitrogen and oxygen enrichment, air and natural gas dehumidification, etc. and has become a popular green separation technology.

[0003] Self-polymerizing microporous polymer membranes (PIMs) are an important part of membrane separation devices, which determine the overall performance of the final separation assembly. Currently, commercially available separation membrane materials include polysulfone (PSF), polycarbonate (PC), cellulose (CA), polyarylether (PAE), and polyimide (PI), etc. As a special engineering plastic in the field of high polymer materials, PI has attracted more and more attention in the fields of microelectronics, flexible display, and membrane separation in recent years due to its low water absorption, high creep resistance, high heat resistance, high strength, high modulus, and chemical stability. In particular, its superior comprehensive physical properties can meet the gas separation and purification under complex conditions of high pressure and high heat. However, through extensive research, the famous membrane separation expert Robeson pointed out that there is a bottleneck problem of mutual restriction between the gas permeation coefficient and the selectivity of the gas pair of the polymer separation membrane [Journal of Membrane Science, 1991, 62, 165-185; Journal of Membrane Science, 2008, 320, 390-400; Journal of Membrane Science, 2015, 475, 101-109; Energy & Environmental Science, 2019, 12, 2733-2740.], that is, high permeation coefficient polymer membranes often exhibit undesirable gas pair selectivity, making it difficult to achieve efficient separation of mixed gases. In addition, the permeation coefficient of the polymer thin film will gradually decrease over time during the long-term separation process, while the selectivity remains basically unchanged or only slightly improves. Moreover, natural gas purification is often carried out under a pressure of 20 bar or even higher in actual working conditions. High pressure CO2 will swell the polymer skeleton, resulting in a decrease in the permeation coefficient of CO2 and the selectivity of CO2 to CH4. This aging behavior and plasticization effect will deteriorate the separation effect and reduce the separation efficiency.

[0004] The crosslinking structure in the prior art has been proved to be able to inhibit the problems of "plasticization" and "aging" existing in the separation membrane in the actual separation process, however, the crosslinking reaction greatly reduces the reprocessing ability of the polymer due to the formation of firm chemical bonds between molecular chains, so that the polymer is difficult to be fused and dissolved, which is not conducive to industrial application. Therefore, exploring a synthesis strategy which can achieve similar crosslinking effect without weakening the processing performance of the polymer is the key to solve the above problems. SUMMARY

[0005] Technical problems to be solved:

[0006] In order to avoid the shortcomings of the prior art, the present application provides a kind of binary amine containing carbazole base unit and its preparation of polyimide gas separation membrane and method, first, a kind of binary amine functional molecule containing carbazole base unit is synthesized, then it is reacted with nitro halogenated benzene to obtain aromatic bis-nitro compound containing hydrogen bond active site (-NH-), finally, the target molecule FNPA diamine is obtained by hydrogenation reduction. After polycondensation of FNPA diamine and binary anhydride, polyamide acid precursor is obtained, and polyimide is obtained after cyclization and dehydration, and finally, the polyimide gas separation membrane containing carbazole base unit and hydrogen bond interaction is obtained by dissolving-tape casting method. The reaction yield of FNPA monomer is significantly improved by palladium metal catalyzed C-N coupling reaction and palladium-carbon catalyzed hydrogenation reduction reaction, the preparation period of the monomer is shortened, and the post-treatment process is simplified. And for the first time, a polyimide gas separation membrane material containing carbazole base unit and hydrogen bond interaction with excellent thermal performance, mechanical properties and gas separation performance is prepared.

[0007] The technical scheme of the present application is: a kind of binary amine containing carbazole base unit, the molecular structure formula of the binary amine is:

[0008]

[0009] In the formula, Y=H, CF3, CH3, Ph; R1=H, CH3, Ph, Br, Cl, I, F.

[0010] A preparation method of a kind of binary amine containing carbazole base unit, the specific steps are as follows:

[0011] Step 1: carbonic acid compound, carbazole derivative, high-boiling-point solvent, cyclohexane are sequentially added into a reaction container, stirred and heated to reflux, water in the system is removed after refluxing at 100-140 DEG C for 2-6h, then cyclohexane is evaporated, the temperature is increased to 150-170 DEG C after adding nitro compound for 2-6h; when the system is cooled to 20-35 DEG C, pour the reaction solution into dilute hydrochloric acid solution, filter and wash the filter cake with distilled water for 2-3 times, and dry at 60-100 DEG C under vacuum for 12-24h to obtain yellow powder product A;

[0012] the molar ratio of the carbonic acid compound to the carbazole derivative is 1-2.0:1;

[0013] the molar ratio of the nitro compound to the carbazole is 1-2.0:1;

[0014] the solute content is controlled to be 15-30 w.t.%;

[0015] Step 2: the prepared powder product A, a palladium-carbon catalyst and a solvent B are sequentially added into a reaction container, stirring is performed, the system is heated to reflux, then hydrazine hydrate is added to continue the reaction for 2-8 hours; after hot filtration, the filtrate is concentrated to obtain a solid product, water washing is performed for 2-4 times, then the product is dried in a vacuum oven at 60-120°C for 12-24 hours to obtain an orange solid product C;

[0016] the addition amount of the palladium-carbon catalyst is determined according to 10-50 mg of the catalyst corresponding to 1 mmol of the nitro group;

[0017] the addition amount of the hydrazine hydrate is determined according to 0.4-0.8 mL of the hydrazine hydrate corresponding to 1 mmol of the nitro group;

[0018] the solute content is controlled to be 10-20 w.t.%;

[0019] Step 3: under an argon atmosphere, a carbonic acid compound, the solid product C, a high-boiling-point solvent and cyclohexane are sequentially added into a reaction container, stirring is performed and the system is heated, water in the system is removed after refluxing at 120-150°C for 2-6 hours; then the cyclohexane is evaporated, the system is heated to 150-170°C after adding a nitro compound, and the reaction is performed for 20-30 hours; when the system is cooled to 20-35°C, the reaction liquid is poured into distilled water to precipitate a solid, suction filtration is performed, the filter cake is washed with distilled water for 2-3 times, and the filter cake is washed with alcohol for 2-3 times to obtain a crude product; the crude product is recrystallized, the filter cake is collected after filtration and dried in a vacuum oven at 60-120°C for 12-24 hours to obtain an orange powder product D;

[0020] the molar ratio of the carbonic acid compound to the product C is 2-3:1;

[0021] the molar ratio of the nitro compound to the product C is 2-3:1;

[0022] the solute content is controlled to be 10-20 w.t.%;

[0023] Step 4: the prepared powder product D, a palladium-carbon catalyst and a solvent B are sequentially added into a reaction container, stirring is performed, the system is heated to reflux, then hydrazine hydrate is added to continue the reaction for 8-18 hours; after hot filtration, the filtrate is concentrated to obtain a solid product, water washing is performed for 2-4 times to obtain a crude product, the crude product is recrystallized, the filter cake is collected after filtration and dried in a vacuum oven at 60-120°C for 12-24 hours to obtain a white powder product E;

[0024] The amount of the palladium catalyst added is determined according to 10-50 mg of catalyst corresponding to 1 mmol of nitro group;

[0025] The amount of the hydrazine hydrate added is determined according to 0.4-0.8 mL of hydrazine hydrate corresponding to 1 mmol of nitro group;

[0026] The solute content is controlled at 10-20 w.t.%;

[0027] Step 5: Under argon atmosphere, a reaction vessel is sequentially charged with a palladium catalyst, a chelating ligand, a powder product E, a nitro compound, a base compound and a solvent I, the system is stirred and heated, and when the temperature is raised to 60-80 °C, the reaction is carried out for 15-30 h; when the system is cooled to 20-35 °C, the filtrate is concentrated after filtration to obtain a crude product; the crude product is recrystallized, the filter cake is collected after filtration and dried in a vacuum oven at 60-120 °C for 12-24 h to obtain a red powder product F;

[0028] The molar ratio of the palladium catalyst to the product E is 0.005-0.01:1;

[0029] The molar ratio of the chelating ligand to the product E is 0.0075-0.015:1;

[0030] The molar ratio of the nitro compound to the product E is 2-2.05:1;

[0031] The molar ratio of the base compound to the product E is 2-3:1;

[0032] The solute content is controlled at 35-45 w.t.%;

[0033] Step 6: The powder product F is dissolved in a solvent B, a palladium-carbon catalyst is added, and the reaction system is placed in a high-pressure reaction kettle for reaction in a hydrogen atmosphere at room temperature for 3-5 h; during the reaction, the hydrogen pressure is maintained at 15-35 bar; after the reaction, the catalyst is filtered off, the solvent B is removed by distillation under reduced pressure to obtain a crude product, and the crude product is recrystallized; the filter cake is collected after filtration and dried in a vacuum oven at 60-120 °C for 12-24 h to obtain an FNPA diamine;

[0034] The solute mass fraction is 5-10 w.t.%;

[0035] The amount of the palladium catalyst added is determined according to 10-50 mg of catalyst corresponding to 1 mmol of nitro group.

[0036] Further technical solutions of the present application are: the carbazole derivative is any one of carbazole, 2,7-dimethylcarbazole, 2,7-diphenylcarbazole, 2,7-dihalogenated carbazole, 1,8-dimethylcarbazole, 1,8-diphenylcarbazole, 1,8-dihalogenated carbazole, 3,6-dimethylcarbazole, 3,6-diphenylcarbazole, 3,6-dihalogenated carbazole, 4,5-dimethylcarbazole, 4,5-diphenylcarbazole, 4,5-dihalogenated carbazole, 2,6-dimethylcarbazole, 2,6-diphenylcarbazole, 2,6-dihalogenated carbazole, 2,5-dimethylcarbazole, 2,5-diphenylcarbazole, 2,5-dihalogenated carbazole, 1,7-dimethylcarbazole, 1,7-diphenylcarbazole, 1,7-dihalogenated carbazole, 1,6-dimethylcarbazole, 1,6-diphenylcarbazole, 1,6-dihalogenated carbazole, 1,5-dimethylcarbazole, 1,5-diphenylcarbazole, 1,5-dihalogenated carbazole, 2,5-dimethylcarbazole, 2,5-diphenylcarbazole, 2,5-dihalogenated carbazole, 3,5-dimethylcarbazole, 3,5-diphenylcarbazole, 3,5-dihalogenated carbazole, or a combination thereof; the halogen element is any one of fluorine, chlorine, bromine, iodine, or a combination thereof.

[0037] Further technical solutions of the present application are: the high-boiling-point solvent is any one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, or a combination thereof.

[0038] The nitro compound is any one of o-nitrohalobenzene, m-nitrohalobenzene, p-nitrohalobenzene, 2-methyl-4-nitrohalobenzene, 3-methyl-4-nitrohalobenzene, 4-nitro-3-trifluoromethylhalobenzene, 4-nitro-2-trifluoromethylhalobenzene, 2-isopropyl-4-nitrohalobenzene, 3-phenyl-4-nitrohalobenzene, 4-nitro-3-phenylhalobenzene, 4-nitro-2-phenylhalobenzene, 3-isopropyl-4-nitrohalobenzene, or a combination thereof; the halogen element is fluorine, chlorine, bromine, or iodine.

[0039] The carbonic compound is any one of sodium carbonate, potassium carbonate, cesium carbonate, or a combination thereof.

[0040] The alkali compound is any one of potassium carbonate, cesium carbonate, sodium ethoxide, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, potassium ethoxide, potassium methoxide, or a combination thereof.

[0041] The solvent B is any one of methanol, tetrahydrofuran, ethyl acetate, acetonitrile, dichloromethane, ethanol, N,N-dimethylformamide, N,N-dimethylacetamide, or a combination thereof.

[0042] The solvent I is any one of methanol, tetrahydrofuran, acetonitrile, dichloromethane, ethanol, 1,4-dioxane, or a combination thereof.

[0043] The further technical scheme of the present application is that the palladium catalyst is any one or combination of palladium acetate, palladium chloride, tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, and bis(acetonitrile)palladium(II) dichloride.

[0044] The further technical scheme of the present application is that the chelating ligand is any one or combination of azide-tetraglycol-succinimide, 2,2-bis(diphenylphosphino)-1,1'-binaphthyl, and ethylenediaminetetraacetic acid.

[0045] A polyimide gas separation membrane prepared by using a diamine containing a carbazole moiety, and the molecular structure is as follows:

[0046]

[0047] wherein Y=H, CF3, CH3, Ph; R1=H, CH3, Ph, Br, Cl, I, F; R represents an aryl group of a dianhydride; the molar ratio of the diamine residue part containing the carbazole moiety is 50%, and the molar ratio of the dianhydride residue part is 50%.

[0048] The further technical scheme of the present application is that the dianhydride is any one or combination of the following compounds, and the chemical structural formula is as follows:

[0049]

[0050] A method for preparing a polyimide gas separation membrane by using a diamine containing a carbazole moiety, and the specific steps are as follows:

[0051] Step 1: under an argon atmosphere, FNPA diamine and a high-boiling-point solvent are sequentially added into a reaction container, and stirring is performed, and the system is cooled after the diamine is dissolved; when the temperature is reduced to 0-10 DEG C, dianhydride is added, and stirring reaction is continuously performed for 10-15 h;

[0052] The molar ratio of the FNPA diamine to the dianhydride is 1:1-1.05; and the solid content is controlled to be 10 w.t.%-20 w.t.%.

[0053] Step 2: under normal temperature, a dehydrating agent and a catalyst are sequentially added into the system of step 1; under an argon atmosphere, stirring reaction is continuously performed for 12-15 h, and then the system is stirred at 50-80 DEG C for 4-8 h; when the system is cooled to 20-35 DEG C, the reaction liquid is poured into an alcohol solution to precipitate a fibrous solid product, the filter cake is filtered and washed with alcohol for 2-4 times, and the filter cake is dried in a vacuum oven at 80-160 DEG C for 12-24 h to obtain a polymer G;

[0054] The molar ratio of the dehydrating agent to the dianhydride is 3-9:1.

[0055] The molar ratio of the catalyst to the dianhydride is 1-3:1.

[0056] Step 3: The polymer G is dissolved in a high-boiling solvent with a solid content of 8-15 w.t.%, and then is cast on a previously leveled glass plate after filtration; the glass plate is placed in a vacuum oven at 50-80 DEG C for 20-30 h, and then the temperature is raised to 120-170 DEG C for 2-6 h; after the temperature is lowered to 20-35 DEG C, the film is removed to obtain a polyimide gas separation film containing carbazole units and hydrogen bonding.

[0057] Further technical solutions of the present application are that the alcohol is any one or combination of ethanol, methanol and isopropanol;

[0058] The dehydrating agent is any one or combination of acetic anhydride, trifluoroacetic anhydride, acetyl chloride or sulfurous chloride;

[0059] The catalyst is any one or combination of triethylamine, trimethylamine, tripropylamine, N,N-dimethylethylamine, 3-methylpyridine, pyridine, N,N-dimethylethanolamine, t-butylpyridine, quinoline, isoquinoline, sodium methoxide or sodium ethoxide.

[0060] Beneficial effects

[0061] The present application has the beneficial effects that the present application optimizes the synthesis method of the FNPA diamine monomer in the prior art from the perspective of molecular structure design and chemical reaction methodology, and first prepares a polyimide gas separation film containing carbazole units and hydrogen bonding. The method can be used to synthesize a series of carbazole-based functional molecules with different molecular structures, enriches the diversity of carbazole-based functional molecules, and prepares a polyimide film material with excellent separation performance.

[0062] The polyimide film prepared by the present application has a thermal decomposition temperature of 500-520 DEG C, a glass transition temperature of 320-340 DEG C, a tensile strength of 100-120 MPa, a tensile modulus of 2.0-2.5 GPa, and an elongation at break of 60-120%. The permeation coefficients of the polyimide film prepared in Example 5 for CO2 and O2 are P (CO2) = 13.9 barrer and P (O2) = 2.8 barrer, and the selectivities for CO2 / CH4 and O2 / N2 gas pairs can reach a (CO2 / CH4) = 46.3 and a (O2 / N2)=6.51, indicating gas separation performance close to the 1991 Robeson upper limit. In the CO2 / CH4 = 1:1 binary gas mixture test, the membrane exhibited good anti-plasticization properties at pressures up to 20 bar, and still showed good separation performance for the CO2 / CH4 mixture. In the O2 / N2 = 22:78 binary gas mixture separation test, the membrane also exhibited good anti-plasticization properties at pressures up to 20 bar, and showed excellent separation performance for the O2 / N2 mixture, with overall separation performance close to the 2008 Robeson upper limit.

[0063] Furthermore, the prepared polyimide separation membrane containing synergistic hydrogen bonding interactions of the carbazole moiety still exhibits stable permeability and relatively constant selectivity after 180 days of physical aging at room temperature, demonstrating outstanding anti-aging performance. The technical route proposed in this invention can provide new synthetic ideas for the molecular structure design and mass production of FNPA monomers, and offer diverse design ideas and raw material bases for the low-cost preparation and potential industrialization of polyimide gas separation membranes containing synergistic hydrogen bonding interactions of the carbazole moiety. This will contribute to promoting the widespread application of polyimide gas separation membranes in the field of separation and purification. Attached Figure Description

[0064] Figure 1 This is a schematic diagram of the synthetic route for preparing FNPA diamine functional monomers through nucleophilic substitution and other reactions in the existing technology;

[0065] Figure 2 This is a schematic diagram of the synthetic route for preparing FNPA diamine functional monomers via CN coupling and other reactions proposed in this invention;

[0066] Figure 3 According to Figure 1 A schematic diagram of monomer structures that may appear during the preparation of FNPA using the shown technical method;

[0067] Figure 4 According to Figure 1 The hydrogen NMR spectrum of the monomer obtained after only one amino group of hydrogen is completely replaced during the preparation of FNPA by the technique shown.

[0068] Figure 5 According to Figure 1 The hydrogen NMR spectrum of the tetrasubstituted monomer during the preparation of FNPA using the technique shown;

[0069] Figure 6 According to Figure 1 The high-resolution mass spectrum of the monomer obtained after only one amino group's hydrogen is completely replaced during the preparation of FNPA using the technique shown.

[0070] Figure 7 According toFigure 1 High resolution mass spectrum of tetra-substituted monomer in the process of preparing FNPA by the technology shown in the figure;

[0071] Figure 8 According to the technology shown in the figure Figure 2 NMR spectrum of FNPA diamine prepared by the technology shown in the figure;

[0072] Figure 9 According to the technology shown in the figure Figure 2 High resolution mass spectrum of FNPA diamine prepared by the technology shown in the figure;

[0073] Figure 10 is a schematic diagram of a synthesis route of a polyimide containing a carbazole moiety and hydrogen bonding;

[0074] Figure 11 is a real photo of a gas separation membrane of a polyimide containing a carbazole moiety and hydrogen bonding prepared in Example 1;

[0075] Figure 12 is the thermal performance of a gas separation membrane of a polyimide containing a carbazole moiety and hydrogen bonding prepared in Example 4: (a) TGA curve, (b) internal friction factor vs. temperature curve;

[0076] Figure 13 is a tensile stress-strain curve of a polyimide containing a carbazole moiety and hydrogen bonding prepared in Example 2;

[0077] Figure 14 is the nitrogen adsorption performance data of a polyimide containing a carbazole moiety and hydrogen bonding prepared in Example 3: (a) adsorption-desorption curve, (b) pore size distribution;

[0078] Figure 15 is a gas separation performance Robeson upper limit diagram of a polyimide containing a carbazole moiety and hydrogen bonding prepared in Example 6;

[0079] Figure 16 is the gas separation performance data of a polyimide containing a carbazole moiety and hydrogen bonding prepared in Example 5: (a) CO2 / CH4=1 / 1 mixed gas separation performance vs. upstream test pressure, (b) CO2 / CH4mixed gas separation upper limit diagram, wherein the solid points are the selectivity and permeability test results of the mixed gas under the conditions of 35℃ and upstream pressure of 2-20 bar;

[0080] Figure 17Gas separation performance data of the polyimide film containing carbazole unit and hydrogen bonding prepared in Example 5: (a) O2 / N2=22 / 78 mixed gas separation performance changes with upstream pressure, (b) O2 / N2=22 / 78 mixed gas separation upper limit diagram, wherein the solid points are the selectivity and permeability test results of the mixed gas under the conditions of 35℃ and upstream pressure of 2-20 bar. DETAILED DESCRIPTION

[0081] The examples described below by reference to the accompanying drawings are exemplary and are intended to explain the present application, and cannot be understood as a limitation of the present application.

[0082] Based on the aging behavior and plasticization effect of the gas separation membrane in the prior art, the separation effect is deteriorated and the separation efficiency is reduced. In addition, the synthesis cycle of the FNPA functional molecule reported at present is long, the overall yield is low, and the post-treatment is difficult, which increases the cost of the FNPA monomer, and it is difficult to mass-produce the monomer and the polyimide gas separation membrane. The present application significantly improves the reaction yield of the FNPA monomer by using palladium metal catalytic C-N coupling reaction and palladium-carbon catalytic hydrogenation reduction reaction, shortens the preparation cycle of the monomer, simplifies the post-treatment process, and for the first time prepares a polyimide gas separation membrane material containing carbazole unit and hydrogen bonding, which has excellent thermal performance, mechanical properties and gas separation performance.

[0083] The carbazole has a rigid structure, and the nitrogen atom in the structure can produce a quadrupole interaction with carbon dioxide, and is easy to be functionalized, and can be used to construct porous adsorption materials and electrochromic materials. Therefore, by using the advantages of the significant steric hindrance and rigid structure of the carbazole molecule, the introduction of the carbazole unit into the polymer molecular skeleton can significantly improve the microporous structure and free volume content of the polymer, and further improve the gas separation flux and the selectivity of the gas pair of the final polymer. The carbazole contains -NH- structure, and the H atom is easy to leave under the influence of the two adjacent benzene rings, so the carbazole is easy to undergo nucleophilic substitution reaction and coupling reaction, and different structure aromatic diamine / dianhydride monomers can be obtained by post-modification. It can be seen that the carbazole monomer has potential application value in constructing polyimide gas separation membrane.

[0084] The hydrogen bond is a supramolecular interaction that can exist between or within molecular chains, which has a force lower than chemical bond but stronger than van der Waals attraction, can form a certain "soft crosslinking" between polymer molecular chains, and can also improve the rigidity of molecular chains, adjust the distance between molecular chains, thereby regulate the gas pair selectivity of the polymer film, improve the plasticization resistance and aging resistance, and achieve the effect similar to chemical crosslinking. Meanwhile, the solubility and reprocessing performance of the polymer are retained. In addition, the introduction of hydrogen bond can improve the mechanical properties of the polymer film material, especially the tensile strength and fracture toughness, which is beneficial to maintaining the integrity of the polymer separation membrane during long-term use. In summary, the polymer film material constructed by carbazole unit and hydrogen bond has potential advantages in the field of gas separation, which can overcome the technical bottleneck that the gas permeation coefficient and selectivity are difficult to be improved simultaneously.

[0085] Based on the above background, the present application is proposed. Through targeted molecular structure design, a diamine monomer 4,4'-bis[(4-aminophenyl)amino]-4"-carbazolyltriphenylamine (FNPA) containing carbazole unit and hydrogen bond active site is prepared in a high yield and a short reaction time. And a PI separation film material containing carbazole unit and hydrogen bond interaction is prepared for the first time using FNPA as raw material. Compared with the synthesis method (technical route as shown in Figure 1 The advantage of the technical route proposed by the present application is that the C-N coupling reaction with higher yield is used in the penultimate step to prepare the double nitro monomer, and then the target molecule FNPA is obtained through palladium-carbon catalytic hydrogenation, and the two-step comprehensive yield can reach more than 87%, as shown in the technical route Figure 2 Although Li et al. can also obtain the FNPA target molecule through nucleophilic substitution and palladium-carbon / hydrazine hydrate reduction, the nucleophilic substitution reaction time is too long (72h), and the two hydrogen atoms on the amino group are easily replaced at the same time. The final target product inevitably mixes four-substituted products and by-products with only one amino group completely replaced (possible monomer molecular structure as shown in Figure 3 This not only reduces the yield of the target product, but also increases the difficulty of purifying the target molecule due to the very close polarity between the by-product and the target molecule. In addition, high-boiling-point solvents (N,N-dimethylformamide) are used in palladium-carbon / hydrazine hydrate reduction, which is difficult to handle and has a long reduction period (72h), ultimately resulting in a two-step comprehensive yield of only 67.6%, which increases the production cost of the monomer. In order to compare the differences between the technical solutions proposed by Li et al. and the present application, the inventors completely prepared the FNPA target molecule according to the experimental method reported by Li et al., and the reaction route is as followsFigure 1 As shown. After the reaction, the inventors separated the final compounds by column chromatography and analyzed their molecular structures using 1H NMR and mass spectrometry. The results are as follows. Figure 4 , Figure 5 , Figure 6 , Figure 7 As shown, in addition to the target product, a tetrasubstituted product and a byproduct with only one amino group completely substituted were also obtained. In contrast, the inventors, using the CN coupling technique proposed in this invention, can obtain the dinitro molecule FNPC in a high yield of 92% in only 24 hours. Further reduction with palladium-catalyzed hydrogenation yields FNPA in over 95%, significantly shortening the reaction time (5 hours vs. 72 hours). The overall yield of the two steps can reach over 87%. The proton NMR spectrum of the FNPA target molecule prepared using the technique proposed in this invention is shown below. Figure 8 As shown, the molecular structure is completely consistent with the theoretical composition, and the high-resolution mass spectrometry results ( Figure 9 This further confirms that the molecular weight of the FNPA monomer prepared using the technical solution proposed in this invention is in complete agreement with the theoretical results, demonstrating that the technical solution proposed in this invention has significant advantages in constructing FNPA diamine monomers.

[0086] The steps for preparing polyimide films using a diamine containing a carbazole moiety in this embodiment are as follows:

[0087] Step 1: Add carbonic acid compound, carbazole derivative, high-boiling solvent, and cyclohexane sequentially to a reaction vessel equipped with a magnetic stirrer, a water separator, and a condenser; start stirring and heat the system, reflux at 100–140°C for 2–6 hours, remove water from the system through the water separator, then distill off the cyclohexane, add a nitro compound, and heat to 150–170°C to react for 2–6 hours; when the system cools to 20–35°C, pour the reaction solution into a dilute hydrochloric acid solution, filter, wash the filter cake 2–3 times with distilled water, and vacuum dry at 60–100°C for 12–24 hours to obtain yellow powder product A;

[0088] The molar ratio of the carbonate compound to the carbazole derivative is 1–2.0:1; the molar ratio of the nitro compound to the carbazole derivative is 1–2.0:1; and the solute content is controlled at 15 w.t.%–30 w.t.%.

[0089] Step 2: Add product A, palladium on carbon catalyst and solvent B sequentially to the reaction vessel containing magnetic particles; after the reaction system is heated to reflux, add hydrazine hydrate and continue the reaction for 2-8 hours; filter while hot and concentrate the filtrate to obtain a solid product, wash with water 2-4 times and dry in a vacuum oven at 60-120℃ for 12-24 hours to obtain orange solid product C;

[0090] The amount of the palladium-carbon catalyst is determined according to 10-50 mg of the catalyst corresponding to 1 mmol of the nitro group;

[0091] The amount of the hydrazine hydrate is determined according to 0.4-0.8 mL of the hydrazine hydrate corresponding to 1 mmol of the nitro group; the solute content is controlled at 10-20 w.t.%;

[0092] Step 3: under argon atmosphere, carbonic compound, product C, high-boiling-point solvent and cyclohexane are sequentially added into a reaction vessel equipped with a magnetic stirrer, a water separator and a condenser; the stirring is started and the system is heated, after refluxing at 120-150 °C for 2-6 h, the water in the system is removed through the water separator, then the cyclohexane is evaporated, the nitro compound is added and the temperature is raised to 150-170 °C for reaction for 20-30 h; when the system is cooled to 20-35 °C, the reaction solution is poured into distilled water to precipitate the solid, the filter cake is washed with distilled water for 2-3 times, then with alcohol for 2-3 times, to obtain the crude product; the crude product is recrystallized, the filter cake is collected and dried in a vacuum oven at 60-120 °C for 12-24 h, to obtain the orange powder product D;

[0093] The molar ratio of the carbonic compound to product C is 2-3:1; the molar ratio of the nitro compound to product C is 2-3:1; the solute content is controlled at 10-20 w.t.%;

[0094] Step 4: product D, palladium-carbon catalyst and solvent B are sequentially added into a reaction vessel equipped with a magnetic stirrer; after the reaction system is heated to reflux, hydrazine hydrate is added for reaction for 8-18 h; the hot filtrate is filtered and concentrated to obtain the solid product, which is washed with water for 2-4 times to obtain the crude product; the crude product is recrystallized, the filter cake is collected and dried in a vacuum oven at 60-120 °C for 12-24 h, to obtain the white powder product E;

[0095] The amount of the palladium-carbon catalyst is determined according to 10-50 mg of the catalyst corresponding to 1 mmol of the nitro group;

[0096] The amount of the hydrazine hydrate is determined according to 0.4-0.8 mL of the hydrazine hydrate corresponding to 1 mmol of the nitro group; the solute content is controlled at 10-20 w.t.%;

[0097] Step 5: under argon atmosphere, palladium catalyst, chelate ligand, product E, nitro compound, base compound and solvent I are sequentially added into a reaction vessel equipped with a magnetic stirrer; the stirring is started and the system is heated, after the temperature is raised to 60-80 °C, reaction is carried out for 15-30 h; when the system is cooled to 20-35 °C, the filtrate is filtered and concentrated to obtain the crude product; the crude product is recrystallized, the filter cake is collected and dried in a vacuum oven at 60-120 °C for 12-24 h, to obtain the red powder product F;

[0098] the molar ratio of the palladium catalyst to product E is 0.005-0.01:1; the molar ratio of the chelating ligand to product E is 0.0075-0.015:1; the molar ratio of the nitro compound to product E is 2-2.05:1; the molar ratio of the base compound to product E is 2-3:1; the solute content is controlled at 35w.t.%-45w.t.%;

[0099] Step 6: product F is dissolved in solvent B, and palladium-carbon catalyst is added, and the reaction system is placed in a high-pressure reaction kettle for reaction in a hydrogen atmosphere at room temperature for 3-5h; the hydrogen pressure is maintained at 15-35bar during the reaction; after the reaction is completed, the catalyst is filtered off, and solvent B is removed by distillation under reduced pressure to obtain a crude product; the crude product is recrystallized, the filter cake is collected after filtration, and is dried in a vacuum oven at 60-120°C for 12-24h to obtain FNPA diamine;

[0100] the solute mass fraction is 5w.t.%-10w.t.%;

[0101] the amount of palladium-carbon catalyst added is determined according to 10-50mg of catalyst corresponding to 1mmol of nitro group;

[0102] Step 7: under an argon atmosphere, FNPA diamine and a high-boiling solvent are sequentially added to a reaction vessel equipped with mechanical stirring, the stirring is started, and after the diamine is dissolved, the system is cooled, and when the temperature is reduced to 0-10°C, a diacid anhydride is added, and the stirring is continued for 10-15h;

[0103] the molar ratio of the FNPA diamine to the diacid anhydride is 1:1-1.05; the solid content is controlled at 10w.t.%-20w.t.%;

[0104] Step 8: under room temperature, a dehydrating agent and a catalyst are sequentially added to the above system, the stirring is continued under an argon atmosphere for 12-15h, and then the system is stirred at 50-80°C for 4-8h; when the system is cooled to 20-35°C, the reaction liquid is poured into an alcohol solution to precipitate fibrous solid product, the filter cake is washed with alcohol for 2-4 times, and the filter cake is dried in a vacuum oven at 80-160°C for 12-24h to obtain polymer G;

[0105] the molar ratio of the dehydrating agent to the diacid anhydride is 3-9:1;

[0106] the molar ratio of the catalyst to the diacid anhydride is 1-3:1;

[0107] Step 9: Dissolve polymer G in high-boiling-point solvent, solid content is controlled at 8w.t.%-15w.t.%, after filtration, flow on the glass plate which is previously adjusted to level; the glass plate is placed in vacuum oven at 50-80℃ for 20-30h, then the temperature is raised to 120-170℃ for 2-6h; after the temperature is reduced to 20-35℃, the film is taken out, to obtain the polyimide gas separation film containing carbazole base unit and hydrogen bond.

[0108] From the above comparison, it can be found that the technical scheme proposed in the present application greatly shortens the preparation period of monomers, at the same time, the overall yield of target molecules is improved to more than 87%, the production cost of monomers is reduced, and it is suitable for batch production. Since the core component of the current membrane separation technology, i.e. polymer membrane, has relatively high cost, the market share of the membrane separation technology is less than 10%, and the key factor determining the cost of the polymer membrane is the comprehensive yield, production period and raw material cost of the monomers. It can be seen that optimizing the synthesis method to improve the yield of monomers is crucial for reducing the cost of polymer membranes and expanding the market share of the membrane separation technology. The technical route proposed in the present application can provide low-cost raw material basis for the molecular structure design and efficient preparation of PI gas separation membrane containing carbazole base unit and hydrogen bond, and is helpful to promote the wide application of PI gas separation membrane in the field of separation and purification.

[0109] The above technical scheme is further described through specific examples as follows.

[0110] Example 1:

[0111] To a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 15.2 g of potassium carbonate, 16.7 g of carbazole, 250 mL of N,N-dimethylacetamide, and 80 mL of cyclohexane were sequentially added. The stirring was started and the system was heated to 100°C for 2 hours. The water in the system was removed through the water separator, and then the cyclohexane was evaporated. After 15.5 g of p-fluoronitrobenzene was added, the temperature was increased to 150°C for 2 hours. When the system was cooled to 20°C, the reaction solution was poured into a dilute hydrochloric acid solution, filtered, and the filter cake was washed twice with distilled water. The filter cake was dried in a vacuum oven at 60°C for 24 hours to obtain yellow powder product A (yield: 97.5%). To a reaction vessel equipped with a magnetic stirrer, 20.2 g of product A, 1.008 g of palladium-carbon catalyst, and 180 mL of ethanol were sequentially added. After the reaction system was heated to reflux, 21 mL of aqueous hydrazine was added and the reaction was continued for 2 hours. After filtration while hot, the filtrate was concentrated to obtain a solid product. After being washed twice with water, the product was dried in a vacuum oven at 60°C for 24 hours to obtain orange solid product C (yield 97.4%). Under an argon atmosphere, to a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 13.0 g of cesium carbonate, 4.7 g of product C, 200 mL of dimethyl sulfoxide, and 40 mL of cyclohexane were sequentially added. The stirring was started and the system was heated to 120°C for 2 hours. The water in the system was removed through the water separator. Then the cyclohexane was evaporated. After 5.6 g of p-fluoronitrobenzene was added, the temperature was increased to 150°C for 30 hours. When the system was cooled to 20°C, the reaction solution was poured into distilled water to precipitate a solid. The solid was filtered, washed twice with distilled water, and then washed three times with methanol to obtain a crude product. The crude product was recrystallized, filtered, and the filter cake was collected and dried in a vacuum oven at 60°C for 24 hours to obtain orange powder product D (yield 70.0%). To a reaction vessel equipped with a magnetic stirrer, 1.7 g of product D, 0.14 g of palladium-carbon catalyst, and 15 mL of ethanol were sequentially added. After the reaction system was heated to reflux, 2.7 mL of aqueous hydrazine was added and the reaction was continued for 8 hours. After filtration while hot, the filtrate was concentrated to obtain a solid product. After being washed twice with water, a crude product was obtained. The crude product was recrystallized, filtered, and the filter cake was collected and dried in a vacuum oven at 60°C for 24 hours to obtain white powder product E (yield 86%). Under an argon atmosphere, to a reaction vessel equipped with a magnetic stirrer, 8.4 mg of palladium acetate, 0.035 g of 2,2-bis(diphenylphosphino)-1,1'-binaphthalene, 2.2 g of product E, 2.50 g of p-iodonitrobenzene, 4.1 g of cesium carbonate, and 20 mL of tetrahydrofuran were sequentially added. The stirring was started and the system was heated to 60°C for 30 hours. When the system was cooled to 35°C, the filtrate was concentrated to obtain a crude product. The crude product was recrystallized, filtered, and the filter cake was collected and dried in a vacuum oven at 120°C for 12 hours to obtain red powder product F (yield 93.5%). 1.0 g of product F was dissolved in 10 mL of ethyl acetate, and 0.09g palladium on carbon catalyst, the reaction system was placed in a high pressure reactor and reacted at room temperature under hydrogen atmosphere for 3h; the hydrogen pressure was maintained at 35 bar during the reaction; after the reaction, the catalyst was filtered off, and the ethyl acetate was removed by distillation under reduced pressure to obtain the crude product, which was recrystallized, the filter cake was collected and dried in a vacuum oven at 60°C for 24h to obtain the FNPA diamine (yield 94.8%); 0.3114g of the FNPA diamine and 1.9mL of N,N-dimethylacetamide were sequentially added to a reaction vessel equipped with mechanical stirring under argon atmosphere, the stirring was started, and after the diamine was dissolved, the system was cooled, and when the temperature dropped to 0°C, 0.1552g of the ODPA diacid anhydride was added, and the stirring was continued for 15h; 0.3g of acetic anhydride and 0.1g of triethylamine were sequentially added to the above system at room temperature, the stirring was continued under argon atmosphere for 15h, and then the system was stirred at 80°C for 4h; when the system was cooled to 35°C, the reaction solution was poured into a methanol solution to precipitate the fibrous solid product, which was filtered and washed with methanol for 4 times, and the filter cake was dried in a vacuum oven at 80°C for 24h to obtain the polymer G; 0.6g of the polymer G was dissolved in N,N-dimethylacetamide, and the solid content was controlled at 15w.t.%, which was filtered and cast on a previously leveled glass plate; the glass plate was placed in a vacuum oven at 50°C for 30h, and then the temperature was raised to 120°C for 6h; after the temperature dropped to 35°C, the film was removed, and a polyimide gas separation film containing carbazole units and hydrogen bonding was obtained.

[0112] Example 2:

[0113] To a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 20.7 g of potassium carbonate, 16.7 g of carbazole, 150 mL of N,N-dimethylacetamide, and 50 mL of cyclohexane were sequentially added. The stirring was started and the system was heated to 140°C and refluxed for 2 hours. The water in the system was removed through the water separator, and then the cyclohexane was distilled off. After 21.2 g of p-fluoronitrobenzene was added, the temperature was increased to 170°C and reacted for 2 hours. When the system was cooled to 35°C, the reaction solution was poured into a dilute hydrochloric acid solution, filtered, and the filter cake was washed with distilled water three times. The filter cake was dried in a vacuum oven at 100°C for 12 hours to obtain yellow powder product A (yield: 98.2%). To a reaction vessel equipped with a magnetic stirrer, 20.2 g of product A, 3.5 g of palladium-carbon catalyst, and 80 mL of ethanol were sequentially added. After the reaction system was heated to reflux, 50 mL of aqueous hydrazine was added and reacted for 2 hours. After filtration while hot, the filtrate was concentrated to obtain a solid product. After water washing four times, the product was dried in a vacuum oven at 120°C for 12 hours to obtain orange solid product C (yield 97.4%). Under an argon atmosphere, to a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 32.6 g of cesium carbonate, 12.9 g of product C, 200 mL of dimethyl sulfoxide, and 40 mL of cyclohexane were sequentially added. The stirring was started and the system was heated to 150°C and refluxed for 6 hours. The water in the system was removed through the water separator, and then the cyclohexane was distilled off. After 14.1 g of p-fluoronitrobenzene was added, the temperature was increased to 170°C and reacted for 20 hours. When the system was cooled to 30°C, the reaction solution was poured into distilled water to precipitate a solid. The solid was filtered, washed with distilled water three times, and then washed with alcohol three times to obtain a crude product. The crude product was recrystallized, filtered, and the filter cake was collected and dried in a vacuum oven at 120°C for 12 hours to obtain orange powder product D (yield 72.1%). To a reaction vessel equipped with a magnetic stirrer, 5.1 g of product D, 0.4 g of palladium-carbon catalyst, and 45 mL of ethanol were sequentially added. After the reaction system was heated to reflux, 4.0 mL of aqueous hydrazine was added and reacted for 15 hours. After filtration while hot, the filtrate was concentrated to obtain a solid product. After water washing four times, a crude product was obtained. The crude product was recrystallized, filtered, and the filter cake was collected and dried in a vacuum oven at 120°C for 12 hours to obtain white powder product E (yield 86.5%). Under an argon atmosphere, to a reaction vessel equipped with a magnetic stirrer, 5.6 mg of palladium acetate, 0.024 g of 2,2-bis(diphenylphosphino)-1,1'-binaphthalene, 2.2 g of product E, 2.56 g of p-iodonitrobenzene, 3.3 g of cesium carbonate, and 15 mL of tetrahydrofuran were sequentially added. The stirring was started and the system was heated to 80°C and reacted for 15 hours. When the system was cooled to 25°C, the filtrate was concentrated to obtain a crude product. The crude product was recrystallized, filtered, and the filter cake was collected and dried in a vacuum oven at 60°C for 24 hours to obtain red powder product F (yield 94.5%). 1.0 g of product F was dissolved in 18 mL of ethyl acetate, and 0.06g palladium on carbon catalyst, the reaction system was placed in a high pressure reactor and reacted at room temperature under hydrogen atmosphere for 4h; the hydrogen pressure was maintained at 25 bar during the reaction; after the reaction, the catalyst was filtered off, and the ethyl acetate was removed by distillation under reduced pressure to obtain the crude product, which was recrystallized, the filter cake was collected and dried in a vacuum oven at 120°C for 12h to obtain the FNPA diamine (yield 95.4%); under argon atmosphere, 0.6228g of FNPA diamine and 10.3mL of N,N-dimethylacetamide were sequentially added to a reaction vessel equipped with mechanical stirring, the stirring was started, and after the diamine was dissolved, the system was cooled, and when the temperature dropped to 0°C, 0.5305g of DNDA diacid anhydride was added, and the stirring was continued for 12h; at room temperature, 0.70g of acetic anhydride and 0.18g of triethylamine were sequentially added to the above system, and the stirring was continued under argon atmosphere for 12h, and then the system was stirred at 50°C for 8h; when the system was cooled to 25°C, the reaction liquid was poured into a methanol solution to precipitate fibrous solid product, which was filtered and washed with methanol 4 times, and the filter cake was dried in a vacuum oven at 80°C for 24h to obtain polymer G; 0.6g of polymer G was dissolved in N,N-dimethylformamide, and the solid content was controlled at 9w.t.%, which was filtered and cast on a previously leveled glass plate; the glass plate was placed in a vacuum oven at 60°C for 25h, and then the temperature was raised to 120°C for 3h; after the temperature dropped to 30°C, the film was removed, and a polyimide gas separation film containing carbazole units and hydrogen bonding was obtained.

[0114] Example 3:

[0115] To a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 17.5 g of potassium carbonate, 16.7 g of carbazole, 200 mL of N,N-dimethylacetamide, and 65 mL of cyclohexane were sequentially added. The stirring was started and the system was heated to 130°C and refluxed for 3 hours. The water in the system was removed through the water separator, and then the cyclohexane was distilled off. After 17.8 g of p-fluoronitrobenzene was added, the temperature was increased to 160°C and reacted for 5 hours. When the system was cooled to 30°C, the reaction solution was poured into a dilute hydrochloric acid solution, filtered, and the filter cake was washed twice with distilled water, and dried at 80°C under vacuum for 18 hours to obtain yellow powder product A (yield: 98.0%). To a reaction vessel equipped with a magnetic stirrer, 20.2 g of product A, 2.1 g of palladium-carbon catalyst, and 110 mL of ethanol were sequentially added. After the reaction system was heated to reflux, 35 mL of aqueous hydrazine was added and reacted for 5 hours. After hot filtration, the filtrate was concentrated to obtain a solid product, which was washed with water three times and dried in a vacuum oven at 100°C for 16 hours to obtain orange solid product C (yield 98.1%). Under argon atmosphere, to a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 48.5 g of cesium carbonate, 12.9 g of product C, 350 mL of dimethyl sulfoxide, and 70 mL of cyclohexane were sequentially added. The stirring was started and the system was heated to 125°C and refluxed for 4 hours. The water in the system was removed through the water separator, and then the cyclohexane was distilled off. After 21.1 g of p-fluoronitrobenzene was added, the temperature was increased to 165°C and reacted for 25 hours. When the system was cooled to 35°C, the reaction solution was poured into distilled water to precipitate a solid, which was filtered, washed with distilled water twice, and washed with methanol three times to obtain a crude product. The crude product was recrystallized, filtered, and the filter cake was collected and dried in a vacuum oven at 100°C for 14 hours to obtain orange powder product D (yield 70.5%). To a reaction vessel equipped with a magnetic stirrer, 5.1 g of product D, 0.5 g of palladium-carbon catalyst, and 25 mL of ethanol were sequentially added. After the reaction system was heated to reflux, 8.0 mL of aqueous hydrazine was added and reacted for 8 hours. After hot filtration, the filtrate was concentrated to obtain a solid product, which was washed with water three times to obtain a crude product. The crude product was recrystallized, filtered, and the filter cake was collected and dried in a vacuum oven at 80°C for 20 hours to obtain white powder product E (yield 84.8%). Under argon atmosphere, to a reaction vessel equipped with a magnetic stirrer, 0.0112 g of palladium acetate, 0.048 g of 2,2-bis(diphenylphosphino)-1,1'-binaphthalene, 2.21 g of product E, 2.52 g of p-iodonitrobenzene, 4.9 g of cesium carbonate, and 17 mL of tetrahydrofuran were sequentially added. The stirring was started and the system was heated to 75°C and reacted for 18 hours. When the system was cooled to 25°C, the filtrate was concentrated to obtain a crude product, which was recrystallized, filtered, and the filter cake was collected and dried in a vacuum oven at 90°C for 20 hours to obtain red powder product F (yield 93.9%). 6.83 g of product F was dissolved in 65 mL of ethyl acetate, and 0.4g of palladium on carbon catalyst, the reaction system was placed in a high pressure reactor and reacted at room temperature under hydrogen atmosphere for 5h; the hydrogen pressure was maintained at 20 bar during the reaction; after the reaction, the catalyst was filtered off, and the ethyl acetate was removed by distillation under reduced pressure to obtain the crude product, which was recrystallized, the filter cake was collected and dried in a vacuum oven at 100°C for 16h to obtain the FNPA diamine (yield 96.1%); 1.2450g of FNPA diamine and 13.6mL of N,N-dimethylacetamide were sequentially added to a reaction vessel equipped with mechanical stirring under argon atmosphere, the stirring was started, and after the diamine was dissolved, the system was cooled, and when the temperature dropped to 5°C, 1.1571g of TPDAN dianhydride was added, and the stirring was continued for 15h; 1.02g of acetic anhydride and 0.23g of triethylamine were sequentially added to the above system at room temperature, and the stirring was continued under argon atmosphere for 15h, and then the system was stirred at 70°C for 5h; when the system was cooled to 20°C, the reaction liquid was poured into an ethanol solution to precipitate fibrous solid product, which was filtered and washed with ethanol 4 times, and the filter cake was dried in a vacuum oven at 160°C for 12h to obtain polymer G; 0.6g of polymer G was dissolved in N,N-dimethylacetamide, and the solid content was controlled at 8w.t.%, which was filtered and cast on a previously leveled glass plate; the glass plate was placed in a vacuum oven at 50°C for 30h, and then the temperature was raised to 140°C for 6h; after the temperature dropped to 20°C, the film was removed, and a polyimide gas separation film containing carbazole units and hydrogen bonding was obtained.

[0116] Example 4:

[0117] To a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 32.8 g of cesium carbonate, 16.7 g of carbazole, 395 mL of N,N-dimethylacetamide, and 80 mL of cyclohexane were sequentially added. The stirring was started and the system was heated to 120°C. After 4 hours, water was removed from the system through the water separator. Then, the cyclohexane was distilled off. After 20.2 g of p-bromonitrobenzene was added, the temperature was increased to 170°C and the reaction was carried out for 3 hours. When the system was cooled to 25°C, the reaction solution was poured into a dilute hydrochloric acid solution. The solution was filtered and the filter cake was washed with distilled water twice. The filter cake was dried in a vacuum oven at 100°C for 14 hours to obtain yellow powder product A (yield: 98.5%). To a reaction vessel equipped with a magnetic stirrer, 23.1 g of product A, 1.6 g of palladium-carbon catalyst, and 95 mL of ethanol were sequentially added. After the reaction system was heated to reflux, 32 mL of aqueous hydrazine was added and the reaction was carried out for 8 hours. After filtration, the filtrate was concentrated to obtain a solid product. After water washing three times, the product was dried in a vacuum oven at 120°C for 14 hours to obtain orange solid product C (yield: 98.4%). Under an argon atmosphere, to a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 32.9 g of cesium carbonate, 12.9 g of product C, 600 mL of dimethyl sulfoxide, and 120 mL of cyclohexane were sequentially added. The stirring was started and the system was heated to 130°C. After 5 hours, water was removed from the system through the water separator. Then, the cyclohexane was distilled off. After 20.2 g of p-bromonitrobenzene was added, the temperature was increased to 165°C and the reaction was carried out for 26 hours. When the system was cooled to 30°C, the reaction solution was poured into distilled water to precipitate a solid. The solid was filtered, washed with distilled water three times, and washed with methanol twice to obtain a crude product. The crude product was recrystallized, filtered, and the filter cake was collected and dried in a vacuum oven at 120°C for 12 hours to obtain orange powder product D (yield: 71.8%). To a reaction vessel equipped with a magnetic stirrer, 5.1 g of product D, 1.0 g of palladium-carbon catalyst, and 40 mL of ethanol were sequentially added. After the reaction system was heated to reflux, 8.0 mL of aqueous hydrazine was added and the reaction was carried out for 12 hours. After filtration, the filtrate was concentrated to obtain a solid product. After water washing four times, a crude product was obtained. The crude product was recrystallized, filtered, and the filter cake was collected and dried in a vacuum oven at 60°C for 24 hours to obtain white powder product E (yield: 86.4%). Under an argon atmosphere, to a reaction vessel equipped with a magnetic stirrer, 5.6 mg of palladium acetate, 0.030 g of 2,2-bis(diphenylphosphino)-1,1'-binaphthalene, 2.21 g of product E, 2.02 g of p-bromonitrobenzene, 3.3 g of cesium carbonate, and 14 mL of tetrahydrofuran were sequentially added. The stirring was started and the system was heated to 60°C. After 30 hours, the system was cooled to 20°C. The filtrate was concentrated to obtain a crude product. The crude product was recrystallized, filtered, and the filter cake was collected and dried in a vacuum oven at 100°C for 18 hours to obtain red powder product F (yield: 94.0%). 6.83 g of product F was dissolved in 65 mL of tetrahydrofuran.4g of palladium on carbon catalyst, the reaction system was placed in a high pressure reactor and reacted at room temperature under hydrogen atmosphere for 5h; the hydrogen pressure was maintained at 15 bar during the reaction; after the reaction, the catalyst was filtered off, and the crude product was obtained by removing tetrahydrofuran under reduced pressure, the crude product was recrystallized, the filter cake was collected and dried in a vacuum oven at 80°C for 16h to obtain FNPA diamine (yield 93.1%); 1.2450g of FNPA diamine and 11mL of N,N-dimethylacetamide were sequentially added to a reaction vessel equipped with mechanical stirring under argon atmosphere, the stirring was started, and after the diamine was dissolved, the system was cooled, and when the temperature dropped to 5°C, 1.2570g of FBDA diacid anhydride was added, and the stirring was continued for 12h; 0.65g of acetic anhydride and 0.25g of triethylamine were sequentially added to the above system at room temperature, and the stirring was continued under argon atmosphere for 12h, and then the system was stirred at 80°C for 4h; when the system was cooled to 20°C, the reaction solution was poured into a methanol solution to precipitate fibrous solid product, which was filtered and washed with methanol for 3 times, and the filter cake was dried in a vacuum oven at 100°C for 18h to obtain polymer G; 0.65g of polymer G was dissolved in N,N-dimethylacetamide, and the solid content was controlled at 15w.t.%, which was filtered and cast on a previously leveled glass plate; the glass plate was placed in a vacuum oven at 60°C for 20h, and then the temperature was raised to 160°C for 4h; after the temperature dropped to 20°C, the film was removed, and a polyimide gas separation film containing carbazole units and hydrogen bonding was obtained.

[0118] Example 5:

[0119] To a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 47.6 g of cesium carbonate, 16.7 g of carbazole, 300 mL of N,N-dimethylacetamide, and 60 mL of cyclohexane were sequentially added. The stirring was started and the system was heated to 110°C and refluxed for 3 hours. The water in the system was removed through the water separator, and then the cyclohexane was distilled off. After 30.3 g of p-bromonitrobenzene was added, the temperature was increased to 168°C and reacted for 4 hours. When the system was cooled to 25°C, the reaction solution was poured into a dilute hydrochloric acid solution, filtered, and the filter cake was washed with distilled water twice, and dried at 80°C under vacuum for 18 hours to obtain yellow powder product A (yield: 96.9%). To a reaction vessel equipped with a magnetic stirrer, 23.1 g of product A, 4.0 g of palladium-carbon catalyst, and 150 mL of ethanol were sequentially added. After the reaction system was heated to reflux, 64 mL of aqueous hydrazine was added and the reaction was continued for 7 hours. After filtering while hot, the filtrate was concentrated to obtain a solid product, which was washed with water three times and dried in a vacuum oven at 110°C for 18 hours to obtain orange solid product C (yield 97.9%). Under argon atmosphere, to a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 49.0 g of cesium carbonate, 12.9 g of product C, 600 mL of dimethyl sulfoxide, and 120 mL of cyclohexane were sequentially added. The stirring was started and the system was heated to 120°C and refluxed for 4 hours. The water in the system was removed through the water separator, and then the cyclohexane was distilled off. After 30.3 g of p-bromonitrobenzene was added, the temperature was increased to 160°C and reacted for 24 hours. When the system was cooled to 25°C, the reaction solution was poured into distilled water to precipitate a solid, which was filtered, washed with distilled water three times, and washed with methanol twice to obtain a crude product. The crude product was recrystallized, filtered, and the filter cake was collected and dried in a vacuum oven at 100°C for 12 hours to obtain orange powder product D (yield 72.4%). To a reaction vessel equipped with a magnetic stirrer, 5.1 g of product D, 0.45 g of palladium-carbon catalyst, and 20 mL of ethanol were sequentially added. After the reaction system was heated to reflux, 16 mL of aqueous hydrazine was added and the reaction was continued for 16 hours. After filtering while hot, the filtrate was concentrated to obtain a solid product, which was washed with water three times to obtain a crude product. The crude product was recrystallized, filtered, and the filter cake was collected and dried in a vacuum oven at 90°C for 20 hours to obtain white powder product E (yield 88.5%). Under argon atmosphere, to a reaction vessel equipped with a magnetic stirrer, 10.0 mg of palladium acetate, 0.050 g of 2,2-bis(diphenylphosphino)-1,1'-binaphthalene, 2.20 g of product E, 2.07 g of p-bromonitrobenzene, 4.1 g of cesium carbonate, and 13 mL of tetrahydrofuran were sequentially added. The stirring was started and the system was heated to 65°C and reacted for 28 hours. When the system was cooled to 20°C, the filtrate was concentrated to obtain a crude product, which was recrystallized, filtered, and the filter cake was collected and dried in a vacuum oven at 80°C for 18 hours to obtain red powder product F (yield 94.7%). 6.83 g of product F was dissolved in 65 mL of tetrahydrofuran, and 1.The reaction mixture was placed in a high pressure reactor and stirred at room temperature under hydrogen atmosphere for 2 h. The hydrogen pressure was maintained at 35 bar during the reaction. After the reaction, the catalyst was filtered off and the tetrahydrofuran was removed by distillation under reduced pressure. The crude product was recrystallized and the filter cake was collected and dried in a vacuum oven at 60 °C for 24 h to obtain the FNPA diamine (yield 94.6%). To a reaction vessel equipped with a mechanical stirrer, 1.2450 g of the FNPA diamine and 11 mL of N,N-dimethylacetamide were added under argon atmosphere. The stirring was started and the temperature was lowered to 0 °C. Then, 0.8885 g of 6FDA diacid anhydride was added and the stirring was continued for 14 h. To the above reaction mixture, 0.75 g of acetic anhydride and 0.28 g of triethylamine were added at room temperature and the stirring was continued for 15 h under argon atmosphere. Then, the reaction mixture was stirred at 70 °C for 5 h. After the reaction mixture was cooled to 25 °C, the reaction solution was poured into methanol to precipitate the fibrous solid product. The product was filtered and the filter cake was washed with methanol three times. The filter cake was dried in a vacuum oven at 110 °C for 13 h to obtain the polymer G. The polymer G (0.58 g) was dissolved in N,N-dimethylacetamide to give a solid content of 12 w.t.%. The solution was cast on a glass plate. The glass plate was placed in a vacuum oven at 70 °C for 20 h and then the temperature was increased to 140 °C for 5 h. After the temperature was decreased to 25 °C, the film was removed and a polyimide gas separation membrane containing carbazole units and hydrogen bonding was obtained.

[0120] Gas permeability data (Barrer) for He, H2, CO2, O2, N2, CH4before and after aging for 180 days for the polyimide gas separation membrane containing carbazole units and hydrogen bonding prepared in Example 5

[0121]

[0122] Selectivity data for CO2 / CH4, CO2 / N2, O2 / N2, H2 / N2and H2 / CH4gas pairs before and after aging for 180 days for the polyimide gas separation membrane containing carbazole units and hydrogen bonding prepared in Example 5

[0123]

[0124] Example 6:

[0125] To a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 38.8 g of cesium carbonate, 16.7 g of carbazole, 290 mL of N,N-dimethylacetamide, and 60 mL of cyclohexane were sequentially added. The stirring was started and the system was heated to 110°C. After 4 hours of reflux, water in the system was removed through the water separator. Then, the cyclohexane was distilled off. After 25.5 g of p-bromonitrobenzene was added, the temperature was increased to 150°C and the reaction was carried out for 3 hours. When the system was cooled to 20°C, the reaction solution was poured into a dilute hydrochloric acid solution. Filtration was performed and the filter cake was washed with distilled water for 3 times. The filter cake was dried in a vacuum oven at 100°C for 15 hours to obtain yellow powder product A (yield: 98.2%). To a reaction vessel equipped with a magnetic stirrer, 23.1 g of product A, 2.8 g of palladium-carbon catalyst, and 110 mL of ethanol were sequentially added. After the reaction system was heated to reflux, 45 mL of aqueous hydrazine was added and the reaction was continued for 5 hours. After filtration at high temperature, the filtrate was concentrated to obtain a solid product. After water washing for 2 times, the product was dried in a vacuum oven at 90°C for 18 hours to obtain orange solid product C (yield: 96.9%). Under argon atmosphere, to a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 40.5 g of cesium carbonate, 12.9 g of product C, 400 mL of dimethyl sulfoxide, and 80 mL of cyclohexane were sequentially added. The stirring was started and the system was heated to 140°C. After 4 hours of reflux, water in the system was removed through the water separator. Then, the cyclohexane was distilled off. After 25.2 g of p-bromonitrobenzene was added, the temperature was increased to 155°C and the reaction was carried out for 28 hours. When the system was cooled to 25°C, the reaction solution was poured into distilled water to precipitate a solid. Filtration was performed. The filter cake was washed with distilled water for 2 times and with methanol for 2 times to obtain a crude product. The crude product was recrystallized. The filter cake was collected after filtration and dried in a vacuum oven at 100°C for 15 hours to obtain orange powder product D (yield: 72.7%). To a reaction vessel equipped with a magnetic stirrer, 5.1 g of product D, 0.8 g of palladium-carbon catalyst, and 32 mL of ethanol were sequentially added. After the reaction system was heated to reflux, 11 mL of aqueous hydrazine was added and the reaction was continued for 17 hours. After filtration at high temperature, the filtrate was concentrated to obtain a solid product. After water washing for 3 times, a crude product was obtained. The crude product was recrystallized. The filter cake was collected after filtration and dried in a vacuum oven at 80°C for 24 hours to obtain white powder product E (yield: 87.2%). Under argon atmosphere, to a reaction vessel equipped with a magnetic stirrer, 8.8 mg of palladium acetate, 0.038 g of 2,2-bis(diphenylphosphino)-1,1'-binaphthalene, 2.19 g of product E, 2.25 g of 2-chloro-5-nitrotolyl trifluoroborate, 3.6 g of cesium carbonate, and 12 mL of tetrahydrofuran were sequentially added. The stirring was started and the system was heated to 70°C. After 24 hours of reaction, the system was cooled to 25°C. Filtration was performed and the filtrate was concentrated to obtain a crude product. The crude product was recrystallized. The filter cake was collected after filtration and dried in a vacuum oven at 110°C for 16 hours to obtain red powder product F (yield: 93.5%). 8.17 g of product F was dissolved in 80 mL of a mixed solution of tetrahydrofuran / ethyl acetate = 1 / 1.8 g of palladium on carbon catalyst, the reaction system was placed in a high pressure reactor and reacted at room temperature under hydrogen atmosphere for 5 h; the hydrogen pressure was maintained at 25 bar during the reaction; after the reaction, the catalyst was filtered off, the mixed solution of tetrahydrofuran and ethyl acetate was removed by distillation under reduced pressure, and then the crude product was obtained; the crude product was recrystallized, the filter cake was collected and dried in a vacuum oven at 90 °C for 14 h to obtain the FNPA diamine (yield 94.3%); 1.5175 g of FNPA diamine and 14 mL of N,N-dimethylacetamide were sequentially added to a reaction vessel equipped with mechanical stirring under argon atmosphere, the stirring was started, and after the diamine was dissolved, the system was cooled, and when the temperature dropped to 3 °C, 1.1110 g of 6FDA diacid anhydride was added, and the stirring reaction was continued for 14 h; 1.50 g of acetic anhydride and 0.45 g of triethylamine were sequentially added to the above system at room temperature, and the stirring reaction was continued under argon atmosphere for 14 h, and then the system was stirred at 70 °C for 5 h; after the system was cooled to 20 °C, the reaction solution was poured into an ethanol solution to precipitate a fibrous solid product, which was filtered and washed with ethanol 4 times, and the filter cake was dried in a vacuum oven at 150 °C for 12 h to obtain the polymer G; 0.60 g of polymer G was dissolved in N,N-dimethylacetamide, and the solid content was controlled at 10 w.t.%, which was filtered and cast on a previously leveled glass plate; the glass plate was placed in a vacuum oven at 70 °C for 25 h, and then the temperature was raised to 140 °C for 4 h; after the temperature dropped to 25 °C, the film was removed to obtain a polyimide gas separation film containing carbazole units and hydrogen bonding.

[0126] Gas permeability and selectivity data of the polyimide film containing carbazole units and hydrogen bonding prepared in Example 6 for pure CO2, CH4, and CO2 / CH4 (50 / 50) mixed gas at 35 °C and 2-20 bar pressure

[0127]

[0128] Gas permeability and selectivity data of the polyimide film containing carbazole units and hydrogen bonding prepared in Example 6 for pure O2, N2, and O2 / N2 (22 / 78) mixed gas at 35 °C and 2-20 bar pressure

[0129]

[0130]

[0131] Example 7:

[0132] To a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 38.8 g of cesium carbonate, 16.7 g of carbazole, 300 mL of N,N-dimethylacetamide, and 60 mL of cyclohexane were sequentially added; the stirring was started and the system was heated, after refluxing at 120°C for 5 h, the water in the system was removed through the water separator, then the cyclohexane was distilled off, 25.1 g of p-bromonitrobenzene was added, and the temperature was raised to 160°C for reaction for 4 h; when the system cooled to 28°C, the reaction solution was poured into a dilute hydrochloric acid solution, filtered, and the filter cake was washed twice with distilled water, and dried at 80°C under vacuum for 15 h to obtain yellow powder product A (yield: 96.8%); To a reaction vessel equipped with a magnetic stirrer, 23.1 g of product A, 3.2 g of palladium-carbon catalyst, and 130 mL of ethanol were sequentially added; after the reaction system was heated to reflux, 48 mL of aqueous hydrazine was added and the reaction was continued for 4 h; after hot filtration, the filtrate was concentrated to obtain a solid product, which was washed with water 3 times and dried in a vacuum oven at 100°C for 14 h to obtain orange solid product C (yield 97.1%); under argon atmosphere, to a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 43.6 g of cesium carbonate, 12.9 g of product C, 470 mL of dimethyl sulfoxide, and 95 mL of cyclohexane were sequentially added; the stirring was started and the system was heated, after refluxing at 130°C for 4 h, the water in the system was removed through the water separator; then the cyclohexane was distilled off, 26.8 g of p-bromonitrobenzene was added, and the temperature was raised to 165°C for reaction for 25 h; when the system cooled to 30°C, the reaction solution was poured into distilled water to precipitate a solid, which was filtered, washed with distilled water 3 times, and washed with methanol 3 times to obtain a crude product; the crude product was recrystallized, the filter cake was collected and dried in a vacuum oven at 120°C for 15 h to obtain orange powder product D (yield 70.9%); To a reaction vessel equipped with a magnetic stirrer, 5.1 g of product D, 0.65 g of palladium-carbon catalyst, and 30 mL of ethanol were sequentially added; after the reaction system was heated to reflux, 13 mL of aqueous hydrazine was added and the reaction was continued for 18 h; after hot filtration, the filtrate was concentrated to obtain a solid product, which was washed with water 4 times to obtain a crude product, which was recrystallized, the filter cake was collected and dried in a vacuum oven at 90°C for 24 h to obtain white powder product E (yield 86.9%); according to the preparation route reported in the literature [Dyes and Pigments, 2020, 173, 107995.], 7.0 g of product E, 8.3 g of p-fluoronitrobenzene, and 7.3g triethylamine was added into a round bottom flask and stirred at room temperature for 5-10 minutes, then the temperature was raised to 120°C for 72 hours. After the reaction system was cooled to 25°C, it was filtered under suction, and the filter cake was washed with distilled water 4 times and methanol 4 times to obtain a crude product. The crude product was purified by column chromatography, and it was found that the yield of the red powder product F was only 20%. Nuclear magnetic resonance and mass spectrometry results showed that a large amount of one-end double-substituted product and four-substituted product appeared in the crude product, proving that the technical scheme provided by Li et al. cannot obtain pure FNPA-based double-nitro monomers, while the technical scheme provided by the present application can efficiently construct FNPA diamine. Nuclear magnetic resonance and mass spectrometry results show that the diamine has an accurate chemical structure and high purity, as shown in. Figure 8

[0133] Example 8:

[0134] ​To a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 38.4 g of cesium carbonate, 16.7 g of carbazole, 310 mL of N,N-dimethylacetamide, and 60 mL of cyclohexane were sequentially added. The stirring was started and the system was heated to 130 °C and refluxed for 6 h. After the water in the system was removed through the water separator, the cyclohexane was distilled off. After 27.1 g of p-bromonitrobenzene was added, the temperature was raised to 160 °C and reacted for 5 h. When the system cooled to 25 °C, the reaction solution was poured into a dilute hydrochloric acid solution, filtered, and the filter cake was washed with distilled water three times, and dried at 90 °C under vacuum for 16 h to obtain yellow powder product A (yield: 96.9%). To a reaction vessel equipped with a magnetic stirrer, 23.1 g of product A, 3.3 g of palladium-carbon catalyst, and 120 mL of ethanol were sequentially added. After the reaction system was heated to reflux, 49 mL of aqueous hydrazine was added and the reaction was continued for 7 h. After filtering while hot, the filtrate was concentrated to obtain a solid product, which was washed with water three times and dried in a vacuum oven at 120 °C for 14 h to obtain orange solid product C (yield 96.8%). Under an argon atmosphere, to a reaction vessel equipped with a magnetic stirrer and a water separator and a condenser, 41.2 g of cesium carbonate, 12.9 g of product C, 460 mL of dimethyl sulfoxide, and 90 mL of cyclohexane were sequentially added. The stirring was started and the system was heated to 140 °C and refluxed for 4 h. After the water in the system was removed through the water separator, the cyclohexane was distilled off. After 28.8 g of p-bromonitrobenzene was added, the temperature was raised to 160 °C and reacted for 28 h. When the system cooled to 25 °C, the reaction solution was poured into distilled water to precipitate a solid, which was filtered, washed with distilled water three times, and washed with methanol three times to obtain a crude product. The crude product was recrystallized, the filter cake was collected and dried in a vacuum oven at 100 °C for 16 h to obtain orange powder product D (yield 71.6%). To a reaction vessel equipped with a magnetic stirrer, 5.1 g of product D, 0.9 g of palladium-carbon catalyst, and 35 mL of ethanol were sequentially added. After the reaction system was heated to reflux, 14 mL of aqueous hydrazine was added and the reaction was continued for 15 h. After filtering while hot, the filtrate was concentrated to obtain a solid product, which was washed with water four times to obtain a crude product. The crude product was recrystallized, the filter cake was collected and dried in a vacuum oven at 80 °C for 22 h to obtain white powder product E (yield 87.2%). According to the reported preparation route [Dyes and Pigments, 2020, 173, 107995.], 7.0 g of product E, 8.3 g of p-fluoronitrobenzene, and 7.3 g of triethylamine were sequentially added to a round-bottom flask and stirred at room temperature for 5-10 min. Then the temperature was raised to 130 °C and reacted for 72 h. After the reaction system was cooled to 25 °C, it was filtered, the filter cake was washed with distilled water five times, and with methanol three times to obtain a crude product. The crude product was purified by column chromatography, and the yield of red powder product F was only 18%. Nuclear magnetic resonance and mass spectrometry results also showed that a large amount of a byproduct in which the hydrogen in one amino group was completely replaced and a tetra-substituted product appeared in the crude product.

[0135] Although the embodiments of the present application have been shown and described above, it is understood that the above-described embodiments are exemplary and are not to be construed as limiting the present application, and that changes, modifications, substitutions and variations can be made by those skilled in the art without departing from the spirit and scope of the present application.

Claims

1. A binary amine comprising a carbazolyl moiety, characterized in that: The molecular structure of the diamine is: Wherein, Y=CF3, CH3, Ph; R1=CH3, Ph, Br, Cl, I, F.

2. A process for the preparation of the binary amine comprising a carbazolyl moiety according to claim 1, characterized in that The specific steps are as follows: Step 1: In a reaction vessel, carbonic compound, carbazole derivative, high boiling point solvent, cyclohexane are added in sequence, stirred and heated to reflux, water in the system is removed after refluxing at 100-140℃ for 2-6 h, then cyclohexane is evaporated, after adding nitro compound, the temperature is raised to 150-170℃ for reaction for 2-6 h; when the system is cooled to 20-35℃, the reaction liquid is poured into dilute hydrochloric acid solution, filtered and the filter cake is washed with distilled water for 2-3 times, and dried at 60-100℃ under vacuum for 12-24 h to obtain yellow powder product A; The molar ratio of the carbonic compound to the carbazole derivative is 1-2.0:1; The molar ratio of the nitro compound to the carbazole is 1-2.0:1; The solute content is controlled at 15 w.t.%-30 w.t.%; Step 2: The prepared powder product A, palladium-carbon catalyst and solvent B are added in sequence into a reaction vessel, stirred, the system is heated to reflux, then hydrazine hydrate is added for further reaction for 2-8 h; after hot filtration, the filtrate is concentrated to obtain solid product, after water washing for 2-4 times, the product is dried in a vacuum oven at 60-120℃ for 12-24 h to obtain orange solid product C; The added amount of the palladium-carbon catalyst is determined according to 10-50 mg of catalyst corresponding to 1 mmol of nitro group; The added amount of the hydrazine hydrate is determined according to 0.4-0.8 mL of hydrazine hydrate corresponding to 1 mmol of nitro group; The solute content is controlled at 10 w.t.%-20 w.t.%; Step 3: Under argon atmosphere, carbonic compound, solid product C, high boiling point solvent, cyclohexane are added in sequence into a reaction vessel, stirred and heated, water in the system is removed after refluxing at 120-150℃ for 2-6 h; then cyclohexane is evaporated, after adding nitro compound, the temperature is raised to 150-170℃ for reaction for 20-30 h; when the system is cooled to 20-35℃, the reaction liquid is poured into distilled water to precipitate solid, filtered, the filter cake is washed with distilled water for 2-3 times and with alcohol for 2-3 times to obtain crude product; the crude product is recrystallized, the filter cake is collected and dried in a vacuum oven at 60-120℃ for 12-24 h to obtain orange powder product D; The molar ratio of the carbonic compound to product C is 2-3:1; The molar ratio of the nitro compound to product C is 2-3:1; The solute content is controlled at 10 w.t.%-20 w.t.%; Step 4: The prepared powder product D, palladium-carbon catalyst and solvent B are added in sequence into a reaction vessel, stirred, the system is heated to reflux, then hydrazine hydrate is added for further reaction for 8-18 h; after hot filtration, the filtrate is concentrated to obtain solid product, after water washing for 2-4 times, the crude product is obtained, the crude product is recrystallized, the filter cake is collected and dried in a vacuum oven at 60-120℃ for 12-24 h to obtain white powder product E; The amount of the palladium catalyst is 10-50 mg per 1 mmol of nitro group; The amount of the hydrazine hydrate is 0.4-0.8 mL per 1 mmol of nitro group; The solute content is controlled to be 10 w.t.%-20 w.t.%; Step 5: Under an argon atmosphere, a reaction vessel is sequentially charged with a palladium catalyst, a chelating ligand, a powder product E, a nitro compound, a base compound and a solvent I, the system is stirred and heated, and when the temperature is raised to 60-80℃, the reaction is carried out for 15-30 h; when the system is cooled to 20-35℃, the filtrate is concentrated after filtration to obtain a crude product; the crude product is recrystallized, the filter cake is collected after filtration and dried in a vacuum oven at 60-120℃ for 12-24 h to obtain a red powder product F; The molar ratio of the palladium catalyst to the product E is 0.005-0.01:1; The molar ratio of the chelating ligand to the product E is 0.0075-0.015:1; The molar ratio of the nitro compound to the product E is 2-2.05:1; The molar ratio of the base compound to the product E is 2-3:1; The solute content is controlled to be 35 w.t.%-45 w.t.%; Step 6: The powder product F is dissolved in a solvent B, a palladium-carbon catalyst is added, and the reaction system is placed in a high-pressure reaction kettle to react in a hydrogen atmosphere at room temperature for 3-5 h; during the reaction, the hydrogen pressure is maintained at 15-35 bar; after the reaction, the catalyst is filtered off, the solvent B is removed by distillation under reduced pressure to obtain a crude product, and the crude product is recrystallized; the filter cake is collected after filtration and dried in a vacuum oven at 60-120℃ for 12-24 h to obtain an FNPA diamine; The solute mass fraction is 5 w.t.%-10 w.t.%; The amount of the palladium catalyst is 10-50 mg per 1 mmol of nitro group.

3. The method of claim 2, wherein the preparation of a binary amine comprising a carbazolyl moiety is characterized by: The carbazole derivative is any one or a combination of carbazole, 2,7-dimethylcarbazole, 2,7-diphenylcarbazole, 2,7-dihalocarbazole, 1,8-dimethylcarbazole, 1,8-diphenylcarbazole, 1,8-dihalocarbazole, 3,6-dimethylcarbazole, 3,6-diphenylcarbazole, 3,6-dihalocarbazole, 4,5-dimethylcarbazole, 4,5-diphenylcarbazole, 4,5-dihalocarbazole, 2,6-dimethylcarbazole, 2,6-diphenylcarbazole, 2,6-dihalocarbazole, 2,5-dimethylcarbazole, 2,5-diphenylcarbazole, 2,5-dihalocarbazole, 1,7-dimethylcarbazole, 1,7-diphenylcarbazole, 1,7-dihalocarbazole, 1,6-dimethylcarbazole, 1,6-diphenylcarbazole, 1,6-dihalocarbazole, 1,5-dimethylcarbazole, 1,5-diphenylcarbazole, 1,5-dihalocarbazole, 2,5-dimethylcarbazole, 2,5-diphenylcarbazole, 2,5-dihalocarbazole, 3,5-dimethylcarbazole, 3,5-diphenylcarbazole, 3,5-dihalocarbazole; and the halogen element is any one or a combination of fluorine, chlorine, bromine and iodine.

4. The method of claim 2, wherein the high-boiling solvent is any one or combination of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide; the nitro compound is any one or combination of o-nitrohalobenzene, m-nitrohalobenzene, p-nitrohalobenzene, 2-methyl-4-nitrohalobenzene, 3-methyl-4-nitrohalobenzene, 4-nitro-3-trifluoromethylhalobenzene, 4-nitro-2-trifluoromethylhalobenzene, 2-isopropyl-4-nitrohalobenzene, 3-phenyl-4-nitrohalobenzene, 4-nitro-3-phenylhalobenzene, 4-nitro-2-phenylhalobenzene, 3-isopropyl-4-nitrohalobenzene; the halogen element is fluorine, chlorine, bromine or iodine; the carbonic compound is any one or combination of sodium carbonate, potassium carbonate, cesium carbonate; the base compound is any one or combination of potassium carbonate, cesium carbonate, sodium ethoxide, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, potassium ethoxide, potassium methoxide; the solvent B is any one or combination of methanol, tetrahydrofuran, ethyl acetate, acetonitrile, dichloromethane, ethanol, N,N-dimethylformamide, N,N-dimethylacetamide; the solvent I is any one or combination of methanol, tetrahydrofuran, acetonitrile, dichloromethane, ethanol, 1,4-dioxane; the palladium catalyst is any one or combination of palladium acetate, palladium chloride, tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, dichlorobis(acetonitrile)palladium(II); the chelating ligand is any one or combination of azide-tetraglycol-succinimidyl, 2,2-bis(diphenylphosphino)-1,1'-binaphthyl, ethylenediaminetetraacetic acid; the molecular structure is as follows: wherein Y = H, CF3, CH3, Ph; R1 = H, CH3, Ph, Br, Cl, I, F; R represents the aryl group of the dianhydride; the molar ratio of the dianhydride residue part is 50%, and the molar ratio of the dianhydride residue part is 50%; the dianhydride is any one or combination of the following compounds, and the chemical structural formula is as follows: the specific steps are as follows: Step 1: under an argon atmosphere, the FNPA diamine and the high-boiling solvent are sequentially added to a reaction vessel, stirred, and the system is cooled after the diamine is dissolved; when the temperature is reduced to 0-10°C, the dianhydride is added, and the stirring reaction is continued for 10-15 h; the molar ratio of the FNPA diamine to the dianhydride is 1:1-1.05; the solid content is controlled at 10 w.t.%-20 w.t.%; Step 2: at room temperature, the dehydrating agent and the catalyst are sequentially added to the system of step 1; under an argon atmosphere, the stirring reaction is continued for 12-15 h, and then the system is stirred at 50-80°C for 4-8 h; when the system is cooled to 20-35°C, the reaction liquid is poured into an alcohol solution to precipitate a fibrous solid product, which is filtered and washed with alcohol for 2-4 times, and the filter cake is dried in a vacuum oven at 80-160°C for 12-24 h to obtain the polymer G. ​ ​ ​ 5. The method of claim 2, wherein the preparation of a binary amine comprising a carbazolyl moiety is characterized by: ​ 6. The method of claim 2, wherein the preparation of a binary amine comprising a carbazolyl moiety is characterized by: ​ 7. A polyimide gas separation membrane prepared from a diamine comprising a carbazolyl moiety, characterized by: ​ ​ ​ 。 8. A method of preparing the polyimide gas separation membrane of claim 7 using a diamine comprising a carbazolyl moiety, characterized by ​ ​ ​ ​ The molar ratio of the dehydrating agent to the dibasic anhydride is 3-9:1; The molar ratio of the catalyst to the dibasic anhydride is 1-3:1; Step 3: Dissolve the polymer G in a high-boiling solvent, the solid content is controlled at 8 w.t.%-15 w.t.%, after filtration, flow onto a previously adjusted to level glass plate; the glass plate is placed in a vacuum oven at 50-80℃ for 20-30 h, then the temperature is raised to 120-170℃ for 2-6 h; after the temperature is reduced to 20-35℃, the film is removed, to obtain a polyimide gas separation film containing carbazole units and hydrogen bonding.

9. The method for preparing a polyimide gas separation membrane according to claim 8, characterized in that: The alcohol is any one or combination of ethanol, methanol, and isopropanol; The dehydrating agent is any one or combination of acetic anhydride, trifluoroacetic anhydride, acetyl chloride, or sulfurous chloride; The catalyst is any one or combination of triethylamine, trimethylamine, tripropylamine, N,N-dimethylethylamine, 3-methylpyridine, pyridine, N,N-dimethylethanolamine, t-butylpyridine, quinoline, isoquinoline, sodium methoxide, or sodium ethoxide.

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