A perfluorosulfonimide resin having ammonia resistance and a method for preparing the same

Abstract

The application discloses a perfluorosulfonimide resin with ammonia resistance, and a preparation method thereof. The preparation method comprises the following steps: dissolving perfluorosulfonic fluoride resin in fluorocarbon solvent to make it swell, so as to obtain a mixed solution; dissolving sulfonamide in a high-boiling-point organic solvent to obtain a monomer solution; under the conditions of no water and no oxygen and stirring, the monomer solution is added dropwise into the obtained mixed solution, and an organic base is used to create an alkaline environment, and the reaction is carried out at a temperature of 80-110 DEG C for 72-120 h, so as to obtain a perfluorosulfonimide resin crude product; the perfluorosulfonimide resin crude product is purified by using water and alcohol as a mixed solvent, and by heating and dissolving in a closed reaction kettle, and then the supernatant is taken and dried, so as to obtain the perfluorosulfonimide resin with ammonia resistance. The application solves the problem that a traditional perfluorosulfonic acid membrane is poisoned in an alkaline environment due to the existence of ammonia, and loses the ability of conducting protons.

Description

Technical Field

[0001] This invention is applied to the field of hydrogen energy technology, specifically hydrogen-ammonia energy conversion. Specifically, it relates to methods for synthesizing sulfonylimide series resins and membranes. Background Technology

[0002] In 2016, Joi Scientific proposed the Hydrogen 2.0™ vision to overcome the limitations of hydrogen use in terms of preparation, storage, transportation, and energy release. In 2017, the Global Ammonia Energy Alliance proposed the new concept of Ammonia = Hydrogen 2.0, aiming to create a new green ammonia energy system to solve the long-tail problem of relying solely on hydrogen energy. Ammonia energy technology is developing from gray ammonia to blue and green ammonia. Globally, 200 million tons of synthetic ammonia are produced annually, with each ton of synthetic ammonia generating 1.8 tons of CO2. my country's annual synthetic ammonia production is 50-60 million tons, accounting for 25-30% of global production. Currently, synthetic ammonia is first-generation gray ammonia; by 2030, the goal is to produce second-generation zero-carbon blue ammonia (natural gas cracking + CO2 capture) and third-generation renewable energy synthetic green ammonia.

[0003] Perfluorosulfonamide resin, as a proton exchange membrane for fuel cells, has better ammonia resistance than traditional sulfonic acid membranes, as well as better conductivity under high temperature and low humidity conditions. It is also a useful material in the field of gas separation.

[0004]

[0005] Nafion:x=6-10,y=1,z=1,m=2

[0006] Aciplex:x=6-8,y=0-1,z=1,m=2-5

[0007] Flemion:x=6-10,y=1,z=1,m=2

[0008] Dow:x=3-10,y=1,z=0,m=2

[0009] In the 1990s, Des Marteau first synthesized perfluorosulfonamide resins using monomer polymerization to improve the conductivity of PEMs. However, this synthesis method has drawbacks, requiring monomer polymerization and involving numerous intermediate steps. These perfluorosulfonic acid membranes (such as Nafion, Aciplex, Flemion, and Dow) can be divided into hydrophobic regions with a hydrophobic fluorocarbon backbone forming a specific crystalline phase, fluorinated ether branched regions, and ionic regions containing sulfonic acid groups. Anionic sulfonate groups are fixed to the perfluorinated backbone through ether branches, reducing anion adsorption on platinum electrocatalysts and exhibiting cation-selective permeability. Simultaneously, the strong electron-withdrawing effect of fluorine atoms increases the acidity of the perfluorosulfonic acid proton exchange membrane, which completely dissociates in water, exhibiting acidity comparable to sulfuric acid, thus increasing the membrane's ionic conductivity. Because the framework uses fluorocarbon polymers, the carbon backbone is protected from oxidation by free radical intermediates in electrochemical reactions. Therefore, these membranes possess high ionic conductivity, chemical stability, thermal stability, and electrochemical stability.

[0010] However, in the context of hydrogen-ammonia fusion technology, in gas separation applications or fuel cells containing ammonia-containing hydrogen-ammonia mixtures, these perfluorosulfonic acid membranes are poisoned in alkaline environments due to the presence of ammonia, losing their ability to conduct protons. Therefore, traditional sulfonic acid membranes cannot completely solve the technical problems of hydrogen-ammonia fusion. There is currently a lack in this field of proton exchange membranes that possess both ammonia resistance and good electrical and thermal conductivity. Summary of the Invention

[0011] The technical problem to be solved by the present invention is to provide a perfluorosulfonyl imide resin with ammonia resistance, which can solve the problem that traditional perfluorosulfonic acid membranes are poisoned in alkaline environments due to the presence of ammonia and lose their ability to conduct protons.

[0012] The technical solution adopted by the present invention to solve the above-mentioned problems is as follows:

[0013] First, this invention provides a perfluorosulfonyl imide resin with ammonia resistance, the structural formula of which is shown in Formula 1:

[0014]

[0015] R1, R2, and R3 are each selected from one or more of the following groups: hydrogen atom, phenyl, fluorine atom, fluoroalkyl, alkyl, amino, imine, cycloalkyl, or other groups with proton conduction sites. R1, R2, and R3 may be the same or different. The ion exchange equivalent (EW) value ranges from 850 to 1100. Preferably, n is 1 to 5, m is 1 to 2, the number of fluorine substitutions in the fluoroalkyl group is 1 to 3, and the number of carbon atoms in the alkyl group is 1 to 5.

[0016] This invention also provides a method for preparing the above-mentioned perfluorosulfonyl imide resin with ammonia resistance, the synthetic route of which is as follows:

[0017]

[0018] In the formula, RH represents an organic base, Solvent a represents a fluorocarbon solvent, and Solvent b represents a high-boiling-point organic solvent (generally above 100℃, so that it can evaporate more slowly when the resin solution is dried to form a film, making the film more uniform).

[0019] The preparation method of the above-mentioned perfluorosulfonamide resin with ammonia resistance includes the following steps:

[0020] (1) Under reflux conditions, the perfluorosulfonyl fluoride film is dissolved in a fluorocarbon solvent to allow it to swell fully, resulting in a mixed solution;

[0021] (2) Dissolve sulfonamide in a high-boiling-point organic solvent to obtain a monomer solution;

[0022] (3) Under anhydrous and oxygen-free conditions and with stirring, the monomer solution obtained in step 2 is added dropwise to the mixed solution obtained in step 1. At the same time, an organic base creates an alkaline environment. The reaction is carried out at a temperature of 80-110℃ for 72-120h to obtain the crude perfluorosulfonyl imide resin product. The alkaline environment created by the organic base can cause the sulfonyl fluoride to dehalogenate and undergo a grafting reaction with the ionized sulfonamide monomer.

[0023] (4) The crude perfluorosulfonamide resin was purified by heating and dissolving it in a closed reactor using water and alcohol as mixed solvents. The supernatant was then taken and dried to obtain perfluorosulfonamide resin particles with ammonia resistance.

[0024] (5) Dissolve the perfluorosulfonamide resin obtained in step (4) in a film-forming solvent, then form a film on the substrate and dry it. The film thickness is controlled at 20-50 μm. Then anneal it. After annealing, the film is acidified in sulfuric acid solution, washed, and dried to obtain the finished perfluorosulfonamide resin film.

[0025] According to the above scheme, in step (1), the perfluorosulfonyl fluoride resin is a perfluorosulfonyl fluoride resin film or a pre-processed film with a film thickness of 20-50 μm; during swelling, the heating temperature is 30-80°C, the mass ratio of the fluorocarbon solvent to the perfluorosulfonyl fluoride resin is 10-30 ml / 1 g, and the solid content is 3.3%-10%, preferably 5%-8%. During the swelling process, the condensation cycle is opened, the condensation cycle temperature is 0-10°C to prevent solvent evaporation, and the heating temperature is preferably 50-80°C, more preferably 60-70°C.

[0026] According to the above scheme, in step (1), the fluorocarbon solvent can swell the perfluorosulfonyl fluoride resin and also has strong hydrophobicity. Preferably, the fluorocarbon solvent includes perfluorinated solvents, partially fluorinated organic solvents, and other halogenated organic solvents, and can be selected from one or more of hexafluorobenzene, hexafluoropropylene trimer, perfluorotributylamine, pentafluorophenol, or perfluoro(methyldecahydronaphthalene).

[0027] According to the above scheme, in step (1), the EW value of the perfluorosulfonyl fluoride resin is 850-1100, and its structural formula is shown in Formula 2. x and y can be selected according to the specific sulfonyl fluoride. Preferably, n is 1-5 and m is 1-2, that is, the number of carbon atoms in the side chain is 4-8. In a preferred example, a perfluorosulfonyl fluoride resin with m=1, n=2, and EW=1050 is selected as the raw material, and its structural formula is shown in Formula 2-1.

[0028]

[0029] According to the above scheme, in step (2), the sulfonamide has the structural formula shown in Formula 3, where R1, R2, and R3 are all selected from one or more of the following groups: hydrogen atom, phenyl, fluorine atom, fluoroalkyl, alkyl, amino, imino, or cycloalkyl, or other groups with proton conduction sites. R1, R2, and R3 may be the same or different. Preferably, the fluoroalkyl group has 1 to 3 fluorine substitutions, and the alkyl group has 1 to 6 carbon atoms.

[0030]

[0031] Furthermore, in step (2), the sulfonamide can preferably be one of the following structures. Among them, trifluoromethanesulfonamide, pentafluoroethanesulfonamide, heptafluoropropanesulfonamide, and other low molecular weight monomers are preferred, as they are beneficial to the dissolution reaction, while the perfluorinated structure is beneficial to the stability of the membrane under working conditions.

[0032]

[0033] According to the above scheme, in step (2), the high-boiling-point organic solvent is one or more of the following in any proportion: acetonitrile, propionitrile, dimethyl sulfoxide, sulfonyl lactone, diethylene glycol dimethyl ether, tetrahydrofuran, dimethylformamide, dioxane, Ph3CH3, etc.

[0034] According to the above scheme, in step (2), the ratio of the volume of the high-boiling-point organic solvent to the molar amount of sulfonamide is 10-30 ml: 1 mol, determined according to the solubility of the monomer. Simultaneously, the stoichiometric ratio of the sulfonamide monomer to perfluorosulfonyl fluoride is (1-1.5): 1 (calculated based on the sulfonyl fluoride resin group), preferably 1: (1.1-1.3). During the dissolution process, the temperature is maintained at 25-100℃ to ensure that the monomeric sulfonamide is fully dissolved in the high-boiling-point organic solvent.

[0035] According to the above scheme, step (3) involves the following reaction:

[0036]

[0037] According to the above scheme, in step (3), before adding the monomer solution and organic base, an inert gas is first introduced to make the reactor an oxygen-free and water-free environment. The inert gas can be nitrogen, argon, krypton, etc., for purging. The flow rate is controlled at 5-15 L / min, and the purging time should not be too long, within the range of 5-15 min. The purging time depends on the size of the container. After that, the constant pressure funnel valves of the monomer solution and organic base are opened, and the dropping rate is controlled at 1-3 drops / s. At the same time, the stirrer is turned on to prevent the local concentration from being too high. The stirrer speed is 100-500 rpm / min, and should not be too fast to avoid the reactants sticking to the reactor wall. At this time, the temperature is raised to 80-110℃, and the reaction is carried out for 72-120 hours.

[0038] According to the above scheme, in step (3), the organic base is selected from one or more of the following: primary amine, secondary amine, tertiary amine, diamine, cyclic amine, aromatic heterocyclic amine, amidine, phosphazene, etc.

[0039] According to the above scheme, in step (4), the mixed solvent is made by mixing water and alcohol in a volume ratio of 1:1 to 1.5; the pressure of the reactor is 0.02 MPa to 0.1 MPa, the temperature is 130 to 180 °C, and the reaction time is 12 to 24 hours.

[0040] According to the above scheme, the specific process of step (5) is as follows: the solid content of the perfluorosulfonamide resin obtained in step (4) is controlled between 5% and 15% in the film-forming solvent. The dissolution is carried out in a pressure-resistant bottle at a temperature of 120 to 150°C and a pressure of 0.01 to 0.05 MPa. The dissolution is carried out for 4 to 12 hours with stirring. After centrifugation, the supernatant is obtained, which is the perfluorosulfonamide resin solution. Then the perfluorosulfonamide resin solution is dried on a glass plate to form a film with a film thickness controlled between 20 and 50 μm. Then gradient annealing is carried out. The annealed film is placed in sulfuric acid solution for acidification. After washing and drying, the finished perfluorosulfonamide resin film is obtained.

[0041] Furthermore, in step (5), the centrifugation speed should not be too high, and should be between 2000 and 5000 rpm / min; the drying temperature of the membrane should be in the range of 30 to 60°C, and the solvent should be evaporated first; the gradient annealing process is as follows: first anneal at 90 to 110°C for 1 to 2 hours, then raise the temperature to 120 to 130°C and anneal for 1 to 2 hours, and then raise the temperature to 140 to 160°C and anneal for 4 to 8 hours; the acidification process is carried out at a temperature of 50 to 90°C and an acidification time of 8 to 12 hours.

[0042] Furthermore, in step (5), the film-forming solvent is one or more of DMF, DMSO, HFB, water, alcohol, etc.

[0043] Compared with the prior art, the beneficial effects of the present invention are:

[0044] First, the grafting method provided by this invention greatly simplifies the process of synthesizing sulfonylimide resin from monomer synthesis to polymerization in Des Matrue. It allows for direct selection of suitable side-chain end-group monomers for hydrogenation-dehalogenation grafting modification with Nafion precursors, shortening the preparation cycle and achieving a high grafting rate. It eliminates the need for amination, double bond protection, and copolymerization with tetrafluoroethylene involved in monomer synthesis, and the preparation process can be entirely transferred from the perfluorosulfonic acid resin manufacturing process. Furthermore, this invention expands the application scenarios of sulfonylimide resins beyond just proton exchange membranes to include gas separation and other applications. Suitable monomers can be selected for modification according to different needs.

[0045] In summary, this invention proposes a novel method for synthesizing perfluorosulfonic imide (PFSI) using the Nafion precursor (perfluorosulfonylfluoride-PFSF), which significantly simplifies traditional synthesis methods and reduces costs. Furthermore, this invention introduces new application scenarios, allowing for the synthesis of structures with different end groups based on the specific application, thus revealing the superior performance of PFSI compared to Nafion. Attached Figure Description

[0046] Figure 1 It has a trifluoromethyl perfluorosulfonyl imide resin structure;

[0047] Figure 2 Trifluoromethyl perfluorosulfonyl imide resin F 19 Each NMR peak corresponds to the position of an F atom;

[0048] Figure 3 To compare the variable humidity test performance of trifluoromethyl perfluorosulfonylimide membrane and perfluorosulfonic acid membrane under conditions without soaking in ammonia water;

[0049] Figure 4 To compare the variable temperature performance of trifluoromethyl perfluorosulfonylimide membrane and perfluorosulfonic acid membrane under conditions without soaking in ammonia water;

[0050] Figure 5 A comparison of performance parameters of trifluoromethyl perfluorosulfonylimide membrane and perfluorosulfonic acid membrane under test conditions of 0.1% wt ammonia concentration and variable humidity. Detailed Implementation

[0051] To better understand the present invention, the following embodiments further illustrate the content of the present invention, but the present invention is not limited to the following embodiments.

[0052] In the following examples, the perfluorosulfonyl fluoride (resin) film was purchased from Wuhan Lvdong, with a thickness of 15 μm and a structural formula of Formula 2-1; the perfluorosulfonic acid (resin) film PFSA was purchased from Wuhan Lvdong, with a thickness of 35 μm and an EW of 1050; the organic base, fluorocarbon solvent, and monomer sulfonamide were purchased from Aladdin.

[0053] Example 1

[0054] A method for preparing a perfluorosulfonamide resin with ammonia resistance specifically includes the following steps:

[0055] (1) Dissolve 5g of a 15μm thick perfluorosulfonyl fluoride resin film with EW=1050 (structural formula 2-1) in 100ml of hexafluorobenzene in a 250ml four-necked flask. The swelling temperature is 55℃, and the reflux temperature is -5℃. The reactive group of perfluorosulfonyl fluoride can be calculated from the formula to be 0.0048 mol.

[0056] (2) Dissolve 0.78 g (0.0052 mol) of trifluoromethylsulfonamide monomer (the molar ratio of perfluorosulfonyl fluoride to trifluoromethylsulfonamide monomer is 1:1.1) in 20 ml of dioxane at a dissolution temperature of 60 °C.

[0057] (3) Argon gas is then introduced into the four-necked flask at a flow rate of 5 L / min for 10 min. After that, the argon gas is turned off, and the monomer solution and triethylamine (organic base) are added dropwise to the reactor. The triethylamine content is 20 ml. The monomer solution is added at a dropping rate of 2 drops / min, and the triethylamine is added at a dropping rate of 1 drop / min. At the same time, the temperature is raised to 90 °C. After the reaction has proceeded for 72 h, the reaction product is removed.

[0058] (4) The reaction product from step (3) was washed five times with anhydrous ethanol. Then, water and ethanol (volume ratio 1:1) were added to a hydrothermal reactor for purification. The temperature was set at 145℃ and the pressure at 0.02-0.03 MPa. After 12 hours of purification and dissolution, the supernatant was taken and centrifuged three times at 2500 rpm / min. The supernatant was then placed in a forced-air drying oven and dried at 80℃ for 24 hours to obtain a perfluorosulfonamide resin with ammonia resistance, namely trifluoromethyl perfluorosulfonamide resin.

[0059] The reaction equation is shown below:

[0060]

[0061] (5) Dissolve 5g of the ammonia-resistant perfluorosulfonamide resin in 50ml of ultra-dry DMF solvent in a pressure-resistant bottle at 120℃ and 0.01-0.05MPa for 12h with stirring. Then centrifuge three times at 2500rpm / min and collect the supernatant to obtain the ammonia-resistant perfluorosulfonamide resin solution. Apply the solution to a glass plate by scraping to form a film. Dry the solvent at 50℃ for 12h and then anneal it in an oven with a gradient temperature increase. First, anneal at 110℃ for 1h, then increase the temperature to 130℃ for 1h, and then increase the temperature to 150℃ for 5h. Finally, acidify the annealed film in 1mol / L sulfuric acid at 80℃ for 12h. Wash three times with deionized water and dry to obtain the final product, trifluoromethyl perfluorosulfonamide resin film (PFSI), the structure of which is shown in Formula 3.

[0062]

[0063] The conductivity of the above-mentioned finished membrane was tested in ammonia solutions of different concentrations: 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.5 wt%, and 1 wt%. The tests were conducted at 30% RH, increasing in 10% increments up to 100% RH, and at a temperature of 80℃. The following tables show the performance characterization results.

[0064] Table 1.1 shows the test performance of the perfluorosulfonamide membrane (PFSI) synthesized in Example 1 under conventional conditions (80°C, RH 30–100%) without immersion in ammonia water; Table 1.2 shows the test performance of the perfluorosulfonic acid membrane (PFSA) synthesized in Example 1 under conventional conditions (80°C, RH 30–100%) without immersion in ammonia water; Table 1.3 shows the test performance of the perfluorosulfonamide membrane (PFSI) synthesized in Example 1 under conventional conditions (100% RH, 30–80°C) without immersion in ammonia water; Table 1.4 shows the test performance of the perfluorosulfonic acid membrane (PFSA) synthesized in Example 1 under conventional conditions (100% RH, 30–80°C) without immersion in ammonia water.

[0065] Table 2.1 shows the performance test results of trifluoromethyl perfluorosulfonylimide membrane (PFSI) after immersion in 0.1% wt ammonia solution for 30 min under conditions of (80℃, RH 30-100%); Table 2.2 shows the performance test results of perfluorosulfonic acid membrane (PFSA) after immersion in 0.1% wt ammonia solution for 30 min under conditions of (80℃, RH 30-100%).

[0066] Table 3 shows the performance test results of the trifluoromethyl perfluorosulfonamide membrane after immersion in ammonia water of different concentrations (0.01% to 1% wt) at 80°C and 100% humidity.

[0067] Table 1.1 Main performance parameters of trifluoromethyl perfluorosulfonylimide membrane (variable humidity)

[0068]

[0069] Table 1.2 Main performance parameters of perfluorosulfonic acid membranes (variable humidity)

[0070]

[0071] Table 1.3 Main performance parameters of trifluoromethyl perfluorosulfonylimide membrane (variable temperature)

[0072]

[0073] Table 1.4 Main performance parameters of perfluorosulfonic acid membranes (variable temperature)

[0074]

[0075]

[0076] Table 2.1 Performance parameters of trifluoromethyl perfluorosulfonylimide membrane against ammonia humidity changes in 0.1% wt ammonia water

[0077]

[0078] Table 2.2 Performance parameters of perfluorosulfonic acid membrane against ammonia humidity changes in 0.1% wt ammonia water

[0079]

[0080] Table 3. Anti-ammonia performance parameters of trifluoromethyl perfluorosulfonylimide membrane in ammonia water of different concentrations.

[0081]

[0082] From Tables 1.1, 1.2, 1.3, and 1.4, and... Figure 3-4 It can be seen that the performance of the perfluorosulfonamide membrane prepared by this invention is close to that of the perfluorosulfonic acid membrane under normal test conditions, and the performance is better under high humidity, with a performance improvement of 10-15%.

[0083] From Tables 2.1 and 2.2 and Figure 5 It can be seen that after being immersed in 0.1% wt ammonia water (NH3·H2O), the performance of the perfluorosulfonamide membrane described in this invention is significantly better than that of the perfluorosulfonic acid membrane, indicating that its resistance to ammonia is stronger than that of the perfluorosulfonic acid membrane.

[0084] Table 3 shows that the perfluorosulfonamide membrane described in this invention exhibits a performance loss of less than 60% when the concentration of ammonia (NH3·H2O) is below 0.01% wt.

[0085] Example 2

[0086] The main difference between Example 2 and Example 1 is that the trifluoromethylsulfonamide monomer in Example 1 is replaced with pentafluoroethylsulfonamide, resulting in a perfluorosulfonamide resin with anti-ammonia ability, namely pentafluoroethyl perfluorosulfonamide resin and its finished film.

[0087] Example 3

[0088] The main difference between Example 3 and Example 1 is that the trifluoromethylsulfonamide monomer in Example 1 is replaced with heptafluoropropylsulfonamide, resulting in a perfluorosulfonamide resin with anti-ammonia ability, namely heptafluoropropyl perfluorosulfonamide resin and its finished film.

[0089] Example 4

[0090] The main difference between Example 4 and Example 1 is that the trifluoromethylsulfonamide monomer in Example 1 is replaced with nonafluorobutylsulfonamide, resulting in a perfluorosulfonamide resin with anti-ammonia ability, namely nonafluorobutyl perfluorosulfonamide resin and its finished film.

[0091] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and modifications without departing from the inventive concept of the present invention, and these all fall within the protection scope of the present invention.

Claims

1. A method for preparing a perfluorosulfonyl imide resin with ammonia resistance, characterized in that, The synthesis route is as follows: Wherein, RH represents an organic base, Solvent a represents a fluorocarbon solvent, and Solvent b represents an organic solvent with a boiling point above 100℃; Choose from one of the following structures: The EW value of the perfluorosulfonamide resin ranges from 850 to 1150, and its structural formula is shown in Formula 1:

2. The method for preparing the perfluorosulfonyl imide resin with ammonia resistance according to claim 1, characterized in that, Includes the following steps: (1) Dissolve the perfluorosulfonyl fluoride resin in a fluorocarbon solvent to make it swell, and obtain a mixed solution; (2) Dissolve sulfonamide in a high-boiling-point organic solvent to obtain a monomer solution; (3) Under anhydrous and oxygen-free conditions and with stirring, the monomer solution obtained in step (2) is added dropwise to the mixed solution obtained in step (1), while an organic base creates an alkaline environment. The reaction is carried out at a temperature of 80-110℃ for 72-120h to obtain the crude perfluorosulfonamide resin product. (4) The crude perfluorosulfonamide resin was purified by heating and dissolving it in a closed reactor using water and alcohol as mixed solvents. The supernatant was then taken and dried to obtain perfluorosulfonamide resin with ammonia resistance.

3. The method for preparing the perfluorosulfonyl imide resin with ammonia resistance according to claim 2, characterized in that, The process also includes step (5): dissolving the perfluorosulfonamide resin obtained in step (4) in a film-forming solvent, then forming and drying the film on a substrate, controlling the film thickness to be 20-50 μm, and then annealing; after annealing, the film is acidified in sulfuric acid solution, washed, and dried to obtain the finished perfluorosulfonamide resin film.

4. The method for preparing the perfluorosulfonyl imide resin with ammonia resistance according to claim 2, characterized in that, In step (1), the perfluorosulfonyl fluoride resin is a perfluorosulfonyl fluoride resin film or a pre-processed film with a film thickness of 20-50 μm; during swelling, the heating temperature is 30-80 °C; in step (2), the high-boiling-point organic solvent is one or a mixture of several of acetonitrile, propionitrile, dimethyl sulfoxide, sulfanilolide, diethylene glycol dimethyl ether, tetrahydrofuran, dimethylformamide, dioxane, and Ph3CH3 in any proportion; in step (3), the organic base is selected from one or a solution of one or more of primary amines, secondary amines, tertiary amines, diamines, cyclic amines, aromatic heterocyclic amines, amidines, and phosphazenes.

5. The method for preparing the perfluorosulfonyl imide resin with ammonia resistance according to claim 2, characterized in that, In step (1), the EW value of the perfluorosulfonyl fluoride resin is 850-1100, and its structural formula is shown in Formula 2: Where n ranges from 1 to 5, and m ranges from 1 to 2.

6. The method for preparing the perfluorosulfonyl imide resin with ammonia resistance according to claim 2, characterized in that, In step (3), before adding the organic base, the reaction chamber is purged with a protective gas to ensure that it is an oxygen-free and water-free environment. Then, the gas flow is stopped, the reflux condenser is turned on, and the organic base is added dropwise. The reflux temperature is between -10 and 15°C. In step (4), the mixed solvent is a mixture of water and alcohol in a volume ratio of 1:1 to 1.

5. The pressure of the reaction vessel is 0.02 MPa to 0.1 MPa, the temperature is 120 to 160°C, and the reaction time is 12 to 24 hours.

7. The method for preparing the perfluorosulfonyl imide resin with ammonia resistance according to claim 2, characterized in that, The specific process of step (5) is as follows: the solid content of the perfluorosulfonamide resin obtained in step (4) is controlled between 5% and 15% in the film-forming solvent. The dissolution is carried out in a pressure-resistant bottle at a temperature of 120-150℃ and a pressure of 0.01-0.05MPa for 4-12 hours under stirring. After centrifugation, the supernatant is obtained, which is the sulfonamide resin solution. Then the sulfonamide resin solution is dried on a glass plate to form a film with a thickness of 20-50μm. Gradient annealing is then performed. The annealed film is placed in a sulfuric acid solution for acidification, and then washed and dried to obtain the finished perfluorosulfonamide resin film.

8. The method for preparing the perfluorosulfonyl imide resin with ammonia resistance according to claim 7, characterized in that, The gradient annealing process is as follows: first, anneal at 90-110℃ for 1-2 hours, then raise the temperature to 120-130℃ and anneal for 1-2 hours, then raise the temperature to 140-160℃ and anneal for 4-8 hours; the acidification process is carried out at 50-90℃ for 8-12 hours.

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