A polymeric phosphonic acid resin dispersion liquid in a wide temperature range, a preparation method and application thereof

Abstract

The present application belongs to the field of fluorine-containing polymer materials, and particularly relates to a polymeric phosphonic resin dispersion liquid, a preparation method and application thereof. The polymeric phosphonic resin dispersion liquid comprises a polymeric phosphonic resin and an organic solvent; the polymeric phosphonic resin is composed of a fluorine-containing olefin unit, a perfluoro vinyl ether phosphonic acid unit, a perfluoro vinyl phosphonic acid unit and a perfluoro olefin sulfonic acid unit. The polymeric phosphonic resin dispersion liquid is uniformly dispersed, and can be used to prepare a perfluoro proton exchange membrane with both sulfonic acid and phosphonic acid proton exchange groups, so that the perfluoro proton exchange membrane has a high ion exchange capacity, is resistant to various chemical media, has high conductivity and proton conductivity, and is very suitable for use in a high-temperature fuel cell or a fuel cell catalyst layer.

Description

Technical Field

[0001] This invention belongs to the field of fluorine-containing polymer materials, specifically relating to a wide-temperature-range polymeric phosphonic acid resin dispersion, its preparation method, and its application. Background Technology

[0002] A fuel cell is a power generation device that directly converts the chemical energy of fuel and oxidant into electrical energy through an electrochemical reaction. It mainly consists of a positive electrode, a negative electrode, an electrolyte, and auxiliary equipment. Due to its advantages such as high efficiency, fast start-up, and low pollution, fuel cells are considered the fourth promising power generation technology after wind, hydro, and solar power, and are a green energy technology that can effectively alleviate the two major problems of "energy shortage" and "environmental pollution" currently facing the world, achieving energy diversification. Proton exchange membrane fuel cells (PEMFCs), in addition to possessing the general characteristics of fuel cells, also feature fast start-up, no electrolyte loss, no corrosion, high energy conversion efficiency, long lifespan, light weight, small size, no pollution, and no infrared radiation. They have broad application prospects in transportation power sources, portable power supplies, and stationary power station power sources.

[0003] Inside a fuel cell, the proton exchange membrane (PEMFC) provides a pathway for proton migration and transport, allowing protons to pass through the membrane from the anode to the cathode, forming a circuit with electron transfer in the external circuit to provide current. Therefore, the performance of the PEMFC plays a crucial role in the performance of the fuel cell, directly affecting its lifespan. To date, the most commonly used PEMFC is still the Nafion membrane from DuPont, a perfluorosulfonic acid membrane. This membrane has high requirements for temperature and water content; the optimal operating temperature for the Nafion series membranes is 70–90°C. Exceeding this temperature causes a sharp decrease in water content and a rapid decline in conductivity, hindering the efforts to improve electrode reaction rates and overcome catalyst poisoning by appropriately increasing the operating temperature. Therefore, there is an urgent need to develop proton exchange resins with high conductivity under high-temperature conditions.

[0004] The development of proton exchange resins with high proton conductivity under high-temperature conditions currently focuses mainly on phosphate-doped aromatic heterocyclic polymer proton exchange membranes. For example, Chinese patent CN112375211A provides a polyaromatic material containing imidazole groups, in which a large number of aromatic and aromatic heterocyclic structures are doped. These membranes are simple to prepare and have strong high-temperature proton conductivity, but they suffer from drawbacks such as low efficiency at low temperatures, inability to start up quickly, poor stability, and short lifespan. Phosphate-doped proton exchange membranes degrade due to the attack of free radicals (·OH or ·OOH) generated in the working environment, making proton conduction difficult below 100°C, resulting in a significant decrease in the mechanical and proton conductivity of the membrane. Therefore, current phosphate-doped polymer proton exchange membranes cannot meet the practical requirements of fuel cells under low-temperature conditions and cannot achieve stable operation of polymer proton exchange membranes over a wide temperature range. Summary of the Invention

[0005] This invention provides a wide-temperature-range polymeric phosphonic acid resin dispersion. This polymeric phosphonic acid resin dispersion is uniformly dispersed and can be used to prepare a perfluorinated proton exchange membrane with both sulfonic acid and phosphoric acid proton exchange groups. This gives the perfluorinated proton exchange membrane a high ion exchange capacity, as well as resistance to various chemical media, high conductivity and proton conductivity, making it very suitable for use in high-temperature fuel cells or fuel cell catalyst layers.

[0006] The specific technical solution is as follows:

[0007] A wide-temperature-range polymeric phosphonic acid resin dispersion includes a wide-temperature-range polymeric phosphonic acid resin and an organic solvent;

[0008] The wide-temperature-range polymeric phosphonic acid resin is composed of fluorinated olefin units, perfluorovinyl ether phosphonic acid units, perfluorovinyl phosphoric acid units, and perfluoroolefin ether sulfonic acid units;

[0009] The structural formula of the wide-temperature-range polymeric phosphonic acid resin is:

[0010] ;

[0011] In the formula, k is an integer from 0 to 3, f is an integer from 1 to 4; g is an integer from 0 to 4; t is an integer from 0 to 3, v is an integer from 1 to 4; a, b and c are integers from 1 to 20, and a', b' and c' are integers from 1 to 3.

[0012] Preferably, k=0-1, f=2; g=2; t=0-1, v=2;

[0013] In the formula, R is —(OCF2) m (CF2) n X, where X is either Cl or F; m and n are integers from 0 to 3;

[0014] x, y, and z satisfy the following conditions: x / (x+y+z)=0.1-0.5, y / (x+y+z)=0.1-0.5, z / (x+y+z)=0.1-0.6.

[0015] In this invention, the organic solvent in the wide-temperature-range polymeric phosphonic acid resin dispersion is one or more of the following: n-propanol, isopropanol, methanol, acetone, N,N-dimethylformamide (DMF), methylamide, acetaldehyde, ethylene glycol, and cyclohexanone.

[0016] In this invention, the mass percentage of the wide-temperature-range polymeric phosphonic acid resin dispersion is 2.5wt%-50wt%, the mass percentage of pure water is 10wt%-95wt%, and the mass percentage of organic solvent is 2.5wt%-87.5wt%.

[0017] Preferably, in the wide-temperature-range polymeric phosphonic acid resin dispersion, the mass percentage of the wide-temperature-range polymeric phosphonic acid resin is 5wt%-40wt%, the mass percentage of pure water is 15wt%-75wt%, and the mass percentage of organic solvent is 5wt%-75wt%.

[0018] In this invention, the micelle size of the wide-temperature-range polymeric phosphonic acid resin dispersion is 100-400 nm.

[0019] The specific steps for preparing the above-mentioned wide-temperature-range polymeric phosphonic acid resin dispersion are as follows:

[0020] S1: Add the above-mentioned wide-temperature-range polymeric phosphonic acid resin, pure water, and organic solvent into the autoclave;

[0021] S2: Under inert gas protection, mechanically stir and dissolve at high temperature. Then stop heating and stirring, and cool to room temperature to obtain a mixed solution.

[0022] S3: After liquid-liquid separation, the mixed solution obtained in step S2 is used to obtain a wide-temperature-range polymeric phosphonic acid resin dispersion.

[0023] In this invention, in step S2 of the method for preparing the wide-temperature-range polymeric phosphonic acid resin dispersion, the inert gas is selected from nitrogen, argon, or xenon.

[0024] The temperature of the mechanical stirring is 120℃~280℃.

[0025] The stirring pressure is 1MPa-5MPa.

[0026] The mechanical stirring time is 2 to 20 hours.

[0027] In step S2 of the method for preparing the wide-temperature-range polymeric phosphonic acid resin dispersion of the present invention, the temperature of the mechanical stirring is 140℃~260℃; the stirring pressure is 2MPa-4MPa; and the mechanical stirring time is 4~15h.

[0028] In this invention, in step S3 of the method for preparing a wide-temperature-range polymeric phosphonic acid resin dispersion, the liquid-liquid separation method includes distillation and extraction separation.

[0029] The extraction and separation method is as follows: the mixed solution is transferred to a separatory funnel, and after extraction and separation by carbon tetrachloride at room temperature and pressure, the lower layer solution is taken out to obtain a wide-temperature-range polymeric phosphonic acid resin dispersion.

[0030] The above-mentioned wide-temperature-range polymeric phosphonic acid resin dispersion or the wide-temperature-range polymeric phosphonic acid resin dispersion prepared by the above preparation method is used in the manufacture of fuel cells, electrolytic systems, and fuel cell catalyst layers.

[0031] The wide-temperature-range polymeric phosphonic acid resin is obtained by a transformation reaction of a polymeric phosphonic acid precursor polymer formed by copolymerization of fluorinated olefin monomers, perfluorovinyl ether phosphonate monomers, perfluorovinyl phosphonate monomers and perfluorosulfonyl fluoroolefin ether monomers.

[0032] Furthermore, the repeating unit of the polymeric phosphonic acid precursor polymer has the following structural formula:

[0033] ;

[0034] In the formula, k is an integer from 0 to 3, f is an integer from 1 to 4, preferably k=0-1 and f=2; g is an integer from 0 to 4, preferably g=2; t is an integer from 0 to 3, v is an integer from 1 to 4, preferably t=0-1 and v=2; a, b, and c are integers from 1 to 20, a', b', and c' are integers from 1 to 3; R is —(OCF2) m (CF2) n X, where X is Cl or F, m and n are integers from 0 to 3; the molar ratio of x, y, and z satisfies the following conditions: x / (x+y+z) = 0.1-0.5, y / (x+y+z) = 0.1-0.5, z / (x+y+z) = 0.1-0.6, p is an integer from 1 to 6, preferably p = 1-3; q is an integer from 1 to 6, preferably q = 1-3.

[0035] The structural formula of the perfluorovinyl ether phosphonate monomer is:

[0036] ;

[0037] Where k is an integer from 0 to 3, preferably k = 0 to 1; f is an integer from 1 to 4, preferably f = 2; p is an integer from 1 to 6, preferably p = 1 to 3.

[0038] The structural formula of the perfluorovinylphosphonate monomer is:

[0039] ;

[0040] Where g = an integer from 0 to 4, preferably g = 0 to 2; q = an integer from 1 to 6, preferably q = 1 to 3.

[0041] The structural formula of the perfluorosulfonyl fluoroene ether monomer is:

[0042] ;

[0043] Where t is an integer from 0 to 3, preferably t = 0 to 1; v is an integer from 1 to 4, preferably v = 2.

[0044] The molar percentages of each polymeric unit in the polymeric phosphate precursor copolymer are as follows: 50-85% for fluorinated olefin polymeric units, 2-25% for perfluorovinyl ether phosphonate polymeric units, 2-25% for perfluorovinyl phosphonate polymeric units, and 1-25% for perfluorosulfonyl fluoroolefin polymeric units.

[0045] Preferably, the molar percentage of each polymeric unit in the polymeric phosphonic acid precursor copolymer is as follows: 60-85% of the total molar percentage of fluorinated olefin polymeric units, 5-20% of the total molar percentage of perfluorovinyl ether phosphonate polymeric units, 5-20% of the total molar percentage of perfluorovinyl phosphonate polymeric units, and 5-20% of the total molar percentage of perfluorosulfonyl fluoroolefin ether polymeric units.

[0046] The number-average molecular weight of the polymeric phosphonic acid polymer is 100,000-600,000, preferably 150,000-500,000, and more preferably 200,000-400,000. The molecular weight distribution index (weight-average molecular weight to number-average molecular weight) of the above-mentioned perfluorinated ionomer is 1.0-2.0, preferably 1.2-1.6.

[0047] This invention also provides a method for preparing the above-mentioned wide-temperature-range polymeric phosphonic acid resin, the specific steps of which are as follows:

[0048] S1: Fluorinated olefins, perfluorovinyl ether phosphonate monomers, perfluorovinyl phosphonate monomers and perfluorosulfonyl fluoroene ether monomers are copolymerized under the action of an initiator to obtain polymeric phosphonic acid precursor polymers.

[0049] S2: The prepared polymeric phosphonic acid precursor polymer is immersed in an alkaline solution to carry out a transformation reaction. After the transformation reaction is completed, the polymer is filtered, acid-washed, and water-washed to obtain a wide-temperature-range polymeric phosphonic acid resin.

[0050] In step S1, the copolymerization reaction includes a step of solution polymerization in a fluorinated solvent, a step of emulsion polymerization in an aqueous phase, or a step of suspension polymerization in an aqueous phase.

[0051] Preferably, the copolymerization reaction is an emulsion polymerization reaction or a suspension polymerization reaction carried out in an aqueous phase.

[0052] In the solution polymerization reaction, the fluorinated solvent is one or more solvents or any combination thereof, which are non-chlorine-atom-containing fluorinated liquid compounds or oligomers; preferably, the fluorinated solvent is a fluorocarbon solvent; more preferably, the fluorinated solvent is CFC-113a.

[0053] The specific steps for carrying out emulsion polymerization or suspension polymerization in an aqueous phase include:

[0054] 1) Add pure water, perfluorovinyl ether phosphonate monomer, perfluorovinyl phosphonate monomer, perfluorosulfonyl fluoroene ether monomer, and emulsifier / dispersant to the reaction vessel;

[0055] 2) Fluoroolefins are introduced into the reactor through a gas metering tank to a pressure of 0.01-10 MPa, preferably 0.2-5 MPa, and more preferably 0.2-2 MPa;

[0056] 3) The reactor is heated to 0-100℃, and an initiator is added to the reaction system through a metering pump to initiate the reaction. Fluorinated olefin monomers and initiators are continuously added to the reactor to maintain the above-mentioned reaction pressure. The reaction time is 0.5-48 hours, preferably 0.5-24 hours, and more preferably 0.5-8 hours.

[0057] 4) At the end of the reaction, stop adding initiator and fluorinated olefin monomers to the reactor. Recover unreacted fluorinated olefin monomers by venting through the reactor venting pipe and recovery tank. A milky white polymer slurry is obtained. The liquid slurry is then passed through the venting system into a post-processing device, where it is filtered and separated by high-speed shearing or other methods to obtain a white polymer powder. This powder is then dried in a 100°C oven to obtain a polymeric phosphonic acid precursor polymer. The perfluorovinyl ether phosphonate monomer, perfluorovinyl phosphonate, and perfluorosulfonyl fluoride monomer in the filtrate are recovered and reused through a recovery system.

[0058] The initiator is selected from one or more of peroxides, perfluoroalkyl peroxides, N2F2, azo compounds or persulfates, and redox systems.

[0059] Preferably, the initiator is selected from, but not limited to, perfluorobutyryl peroxide, perfluoropropoxypropyl peroxide, persulfate, and 15g. -SO2F-perfluoro-2,5,8-trimethyl-3,6,9-trioxa-undecyl peroxide, N2F2 or one of these.

[0060] The amount of the initiator added is 0.01~5%.

[0061] In step 1), an emulsifier is selected when the reaction is emulsion polymerization, and a dispersant is selected when the reaction is suspension polymerization.

[0062] In the emulsion polymerization step, the emulsifier enables better dispersion of perfluorophosphonate monomers and perfluorosulfonyl fluoroolefin monomers in the aqueous phase. The emulsifier is selected from one or any combination of anionic, nonionic, or reactive emulsifiers.

[0063] Preferably, the emulsifier is selected from, but not limited to, sodium dodecyl sulfonate, nonylphenol polyoxyethylene ether, and potassium perfluorovinyl ether sulfonate.

[0064] In the emulsion polymerization step, based on the total weight of the aqueous phase, the mass percentage concentration of the emulsifier in water is 0.01-40%, preferably 0.1-20%; the mass percentage concentration of the perfluorovinyl ether phosphonate monomer in water is 5-60%, preferably 5-50%; the mass percentage concentration of the perfluorovinyl phosphate monomer in water is 5-60%, preferably 5-50%; and the mass percentage concentration of the perfluorosulfonyl fluoroolefin ether monomer in water is 1-60%, preferably 5-50%. In the emulsion polymerization reaction, the fluorinated olefin monomer is introduced into the reaction system in gaseous form.

[0065] In the suspension polymerization reaction step, the dispersant is selected from one or any combination of inorganic salt powder or organic polymer.

[0066] Preferably, the dispersant is selected from, but not limited to, one or more of limestone, calcium carbonate, and methylcellulose.

[0067] Preferably, in the suspension polymerization step, the mass percentage concentration of the dispersant in water is 0.01-40%, more preferably 0.1-20%, the mass percentage concentration of the perfluorovinyl ether phosphonate monomer in water is 5-60%, more preferably 5-50%, the mass percentage concentration of the perfluorovinyl phosphate monomer in water is 5-60%, more preferably 5-50%, and the mass percentage concentration of the perfluorosulfonyl fluoroene ether monomer in water is 1-60%, more preferably 5-50%.

[0068] In step S2, the polymeric phosphonic acid precursor polymer is transformed into a salt or acid form through a transformation reaction to acquire ion exchange function.

[0069] In step S2, the mass ratio of the polymeric phosphonic acid precursor polymer to the alkaline solution is 1:(1-10); the alkaline solution is sodium hydroxide, potassium hydroxide solution, or lithium hydroxide, ammonia, sodium carbonate, potassium carbonate, or lithium carbonate, with a concentration of 0.01-35%, preferably 0.1-25%. The conversion reaction time is 1-144 hours, preferably 5-72 hours, and the conversion temperature is 20-150℃, preferably 20-100℃.

[0070] The pickling solution is a common protic acid or a mixture of protic acids such as nitric acid, sulfuric acid, and hydrochloric acid, with a concentration of 1-30%, preferably 5-20%. The pickling time is 1-144 hours, preferably 5-72 hours, and the pickling temperature is 20-150℃, preferably 20-100℃.

[0071] The wide-temperature-range polymeric phosphonic acid resin can be used in the manufacture of fuel cells, electrolytic systems, fuel cell catalyst layers, and other fields.

[0072] Compared with the prior art, the present invention has at least the following advantages:

[0073] 1. The polymeric phosphoric acid resin dispersion of the present invention is uniformly dispersed and can be used to prepare a perfluorinated proton exchange membrane with both sulfonic acid and phosphoric acid proton exchange groups. This gives the perfluorinated proton exchange membrane a high ion exchange capacity, as well as resistance to various chemical media, high conductivity and proton conductivity, making it very suitable for use in high-temperature fuel cells or fuel cell catalyst layers.

[0074] 2. The copolymer structure of the perfluorinated ionomer described in this invention uses perfluorinated vinyl ether phosphonate units with CO bonds in the side chain and perfluorinated vinyl phosphonate units without CO bonds in the side chain. CO bonds will break and degrade under high temperature conditions. By introducing polymerization units with full C-C bonds in the side chain, the high temperature thermal stability of the entire perfluorinated ionomer can be improved.

[0075] 3. The wide-temperature-range polymeric phosphonic acid resin provided by this invention, through the synergistic effect of perfluorovinyl ether phosphonic acid polymerization unit, perfluorovinyl phosphoric acid polymerization unit, and perfluoroene ether sulfonic acid polymerization unit, solves both the problem of poor thermal stability of existing phosphoric acid-doped perfluorinated ion polymers and the problem of low high-temperature conductivity of perfluorinated ion polymers. It achieves high conductivity of polymeric phosphonic acid resin in the temperature range below freezing point and above boiling point, effectively broadening the temperature range of existing perfluorosulfonic acid resins used in fuel cell membranes. Attached Figure Description

[0076] Figure 1This is a GPC data graph of the polymeric phosphonic acid precursor polymer in Example 1;

[0077] Figure 2 This is a GPC data graph of the polymeric phosphonic acid precursor polymer in Example 2;

[0078] Figure 3 Infrared data of the polymeric phosphonic acid precursor polymer in Example 1;

[0079] Figure 4 The image shows the infrared data of the polymeric phosphonic acid precursor polymer in Example 2. Detailed Implementation

[0080] The following embodiments are further illustrations of the present invention, but the invention is not limited thereto. Unless otherwise specified, the reactors used in each embodiment are 10L stainless steel high-pressure reactors, equipped with temperature sensors, pressure sensors, heating circulation systems, cooling circulation systems, stirring motors, internal cooling water pipes, liquid metering pumps, gas feed valves, liquid feed valves, and material discharge valves from the reactor.

[0081] Unless otherwise specified in the following examples, the ion exchange capacity is the result of the conversion of sulfonyl fluoride to sulfonic acid and phosphonate to phosphorous acid.

[0082] Unless otherwise specified in the embodiments, all percentage contents (%) are mass percentages.

[0083] The perfluoroalkyl initiator used in the synthesis process of this invention can be prepared according to techniques known in the art. The preparation method recommended by this invention can be found in J.Org.Chem., 1982, 47(11): 2009-2013.

[0084] The ammonium persulfate used in the synthesis process of this invention was purchased from Sinopharm Group; the N2F2 gas was purchased from Dongyue Chemical Co., Ltd.

[0085] The tetrafluoroethylene used in the polymerization process of this invention was purchased from Shandong Dongyue Polymer Materials Co., Ltd.; the perfluorovinyl ether phosphonate monomer can be prepared using the methods disclosed in the literature Novel phosphonated perfluorocarbon polymers [J], Masaaki Yamabe et al, European Polymer Journal 36 (2000) 1035–1041, CN200910230218.5; the perfluorovinyl phosphonate monomer can be prepared using the literature Facile Synthesis of Fluorinated Phosphonates Via Photochemical and Thermal Reactions [J], Haridasan K. Nair and Donald J. Burton, J. Am. Chem. Soc. 1997, The perfluorosulfonyl fluoroolefin monomer was prepared by the method disclosed in patent applications CN200910229444.1, CN200910229446.0, CN200910230218.5, and CN201810798170.7.

[0086] Example 1:

[0087] The reactor was cleaned and 5000g of CFC-113a fluorinated organic solvent was added. The stirring device was turned on, and the reactor was evacuated and purged with high-purity nitrogen three times. After testing and confirming that the oxygen content in the reactor was below 1ppm, the reactor was evacuated again. Then, 900g of perfluorovinyl ether phosphonate monomer (CF2=CF-O-CF2CF(CF3)-O-CF2CF2-P=O-(OCH2CH3)2), 275g of perfluorovinyl phosphonate monomer (CF2=CF-CF2-P=O-(OCH2CH3)2), and 325g of perfluorovinyl ether sulfonyl fluoride monomer (CF2=CF) were added to the reactor through the liquid feed valve. After adding tetrafluoroethylene monomer (CF2=CF2-SO2F), the reactor is charged with tetrafluoroethylene monomer to a pressure of 0.5 MPa, and the temperature is raised to 30°C. 3.5 g of perfluorobutyryl peroxide compound (CF3CF2CF2CO-OO-COCF2CF2CF3) is added using a metering pump to initiate the polymerization reaction. Tetrafluoroethylene monomer (CF2=CF2) is continuously introduced to maintain the reaction pressure at 0.5 MPa. 0.85 g of initiator is added to the system every 15 minutes. After 2 hours of reaction, the addition of initiator is stopped, and the reaction is allowed to continue for another 15 minutes before the addition of tetrafluoroethylene monomer is stopped. The reactor is cooled using a cooling circulation system, and unreacted tetrafluoroethylene monomer is recovered using a recovery system. The liquid in the reactor is discharged into a post-treatment system through a discharge valve. The polymer is separated by chloroform solvent through sedimentation and flocculation, and then dried in a 100°C oven to obtain a polymeric phosphonic acid precursor polymer. Chloroform, 113a fluorinated organic solvents, and unreacted perfluorophosphate monomers and perfluorosulfonyl fluoroolefin monomers are recovered and reused through a recycling system.

[0088] Polymer data: via F 19 NMR and IR analyses confirmed it to be a quaternary copolymer. The fluorine NMR integral value showed that the polymer structure contained 58.18% tetrafluoroethylene polymer units, 24.60% perfluorovinyl ether phosphonate polymer units, 8.12% perfluorovinyl phosphonate polymer units, and 9.10% perfluorosulfonyl fluoroene ether polymer units. The total ion exchange capacity of the resin was 1.25 mmol / g dry resin.

[0089] The GPC test showed a molecular weight of 234,000 and a molecular weight distribution value of 1.65.

[0090] IR spectrum: 1468cm -1 This is the absorption peak of the S=O vibration in sulfonyl fluoride; 1294 cm⁻¹ -1 This is the absorption peak for the P=O vibration in phosphonates; 1030 cm⁻¹ -1 The absorption peaks for the COC bond are at 1230 and 1155 cm⁻¹. -1 The two strongest absorptions are caused by CF vibrations; 720cm-1 640cm -1 This is caused by the absorption of the -CF2-CF2- vibration after the copolymerization of tetrafluoroethylene.

[0091] Example 2:

[0092] The reactor was cleaned and 5.0L of deionized water and 200g of sodium dodecylbenzenesulfonate were added. The stirring device was turned on, and the reactor was evacuated and purged with high-purity nitrogen three times. After testing and confirming that the oxygen content inside the reactor was below 1ppm, the reactor was evacuated again. Then, 850g of perfluorovinyl ether phosphate monomer (CF2=CF-O-(CF2)-P=O-(OCH3)2), 850g of perfluorovinyl phosphate monomer (CF2=CF-CF2-P=O-(OC3H7)2), and 200g of perfluorovinyl ether sulfonyl fluoride monomer (CF2=CF-O-CF2CF(CF3)-(CF2)2-SO2F) were added to the reactor through the liquid feed valve. Finally, tetrafluoroethylene monomer was added to the reactor until the pressure reached 0.9 ppm. The pressure was raised to 40℃, and 10g of perfluoropropoxypropyl peroxide compound (CF3CF2CF2OCF(CF3)CO-OO-COCF(CF3)OCF2CF2CF3) was added using a metering pump to initiate the polymerization reaction. Tetrafluoroethylene monomer was continuously introduced to maintain the reaction pressure at 0.9MPa. 2.0g of initiator was added to the system every 20min. After 2.5h of reaction, the addition of initiator was stopped, and the reaction was allowed to continue for another 20min before the addition of tetrafluoroethylene monomer was stopped. The reactor was cooled using a cooling circulation system, and unreacted tetrafluoroethylene monomer was recovered using a recovery system. The milky white slurry in the reactor was discharged into the post-processing system through a discharge valve. After high-speed shear demulsification and coagulation, the mixture was filtered to obtain a white polymer powder, which was dried in a 100℃ oven to obtain a polymeric phosphonic acid precursor polymer. The perfluorophosphate monomer and perfluorosulfonyl fluoroolefin ether monomer in the filtrate were recovered and reused using the recovery system.

[0093] Polymer data: via F 19 NMR and IR analyses confirmed it to be a quaternary copolymer. The fluorine NMR integral value showed that the polymer structure contained 65.28% tetrafluoroethylene polymer units, 13.21% perfluorovinyl ether phosphonate polymer units, 16.31% perfluorovinyl phosphonate polymer units, and 5.20% perfluorosulfonyl fluoroene ether polymer units. The total ion exchange capacity of the resin was 1.53 mmol / g dry resin.

[0094] The GPC test showed a molecular weight of 309,000 and a molecular weight distribution value of 1.63.

[0095] IR spectrum: 1468cm -1This is the absorption peak of the S=O vibration in sulfonyl fluoride; 1296 cm⁻¹ -1 This is the absorption peak for the P=O vibration in phosphonates; 1028 cm⁻¹ -1 The absorption peak for the COC bond is 984 cm⁻¹. -1 Caused by -CF3 vibration; 1228 and 1148 cm -1 The two strongest absorptions are caused by the -CF vibration; 720 cm⁻¹ -1 641cm -1 This is caused by the absorption of the -CF2-CF2- vibration after the copolymerization of tetrafluoroethylene.

[0096] Example 3:

[0097] The reactor was cleaned and 5.0L of deionized water, 125g of sodium dodecylbenzenesulfonate, and 80g of nonylphenol polyoxyethylene ether NP-10 emulsifier were added. The stirring device was turned on, and the reactor was evacuated and purged with high-purity nitrogen three times. After testing and confirming that the oxygen content in the reactor was below 1ppm, the reactor was evacuated again. Then, 375g of perfluorovinyl ether phosphonate monomer (CF2=CF-O-CF2CF(CF3)-O-CF2CF2-P=O-(OCH3)2), 250g of perfluorovinyl phosphonate monomer (CF2=CF-CF2CF2-P=O-(OCH3)2), and 1050g of perfluorovinyl ether sulfonyl fluoride monomer (CF2=CF-O-CF2CF2-SO2F) were added to the reactor through the liquid feed valve. Finally, tetrafluoroethylene monomer was added to the reactor until the pressure reached 3.5. The pressure was raised to 80℃, and 350g of a 10% ammonium persulfate aqueous solution was added using a metering pump to initiate the polymerization reaction. Tetrafluoroethylene monomer was continuously introduced to maintain the reaction pressure at 3.5MPa. After 2 hours of reaction, the initiator was stopped, and the reaction was allowed to continue for 15 minutes before the addition of tetrafluoroethylene monomer was stopped. The reactor was cooled using a cooling circulation system, while unreacted tetrafluoroethylene monomer was recovered using a recovery system. The milky white slurry in the reactor was discharged into the post-processing system through a discharge valve. After high-speed shear demulsification and coagulation, the mixture was filtered to obtain a white polymer powder, which was then dried in a 100℃ oven to obtain the polymeric phosphonic acid precursor polymer. The perfluorophosphonate monomer and perfluorosulfonyl fluoroolefin ether monomer in the filtrate were recovered and reused using the recovery system.

[0098] Polymer data: via F 19 NMR and IR analyses confirmed it to be a quaternary copolymer. Fluorine NMR integral values ​​showed that the polymer structure contained 70.25% tetrafluoroethylene polymer units, 7.25% perfluorovinyl ether phosphonate polymer units, 3.23% perfluorovinyl phosphonate polymer units, and 19.27% ​​perfluorosulfonyl fluoroene ether polymer units. The total ion exchange capacity of the resin was 1.28 mmol / g dry resin.

[0099] The GPC test showed a molecular weight of 325,000 and a molecular weight distribution value of 1.45.

[0100] IR spectrum: 1470cm -1 This is the absorption peak for the S=O vibration in sulfonyl fluoride; 1294 cm⁻¹ -1 The peak at 1028 cm⁻¹ represents the P=O vibration absorption peak in phosphonates; the peak at 1225 and 1150 cm⁻¹ represents the COC bond absorption peak. -1 The two strongest absorptions are caused by CF vibrations; 984 cm -1 Caused by -CF3 vibration; 720cm -1 641cm -1 This is caused by the absorption of the -CF2-CF2- vibration after the copolymerization of tetrafluoroethylene.

[0101] Example 4:

[0102] The reactor was cleaned and 5.0L of deionized water, 150g of sodium dodecylbenzenesulfonate, and 105g of nonylphenol polyoxyethylene ether NP-10 emulsifier were added. The stirring device was turned on, and the reactor was evacuated and purged with high-purity nitrogen three times. After testing and confirming that the oxygen content in the reactor was below 1ppm, the reactor was evacuated again. Then, 1400g of perfluorovinyl ether phosphonate monomer (CF2=CF-O-CF2CF2-P=O-(OCH2CH3)2), 225g of perfluorovinyl phosphonate monomer (CF2=CF-(CF2)3-P=O-(OCH3)2), and 225g of perfluorovinyl ether sulfonyl fluoride monomer (CF2=CF-O-CF2CF2-SO2F) were added to the reactor through the liquid feed valve. Tetrafluoroethylene monomer was then added to the reactor until the pressure reached 1.8MPa. The temperature was raised to 20℃, and the flow rate was controlled at 30cm³ using a gas flow meter. 3 250 mL of N2F2 was introduced into the reactor at a rate of / min to initiate the polymerization reaction. Tetrafluoroethylene monomer was continuously introduced to maintain the reaction pressure at 1.8 MPa. After 4 hours of reaction, the initiator was stopped, and the reaction was allowed to continue for 1 minute before the addition of tetrafluoroethylene monomer was stopped. The reactor was cooled using a cooling circulation system, while unreacted tetrafluoroethylene monomer was recovered using a recovery system. The milky white slurry in the reactor was discharged into a post-processing system through a discharge valve. After demulsification and coagulation using high-speed shearing or other known demulsification methods, the slurry was filtered to obtain a white polymer powder, which was then dried in a 100°C oven to obtain the polymeric phosphonic acid precursor polymer. The perfluorophosphonate monomer and perfluorosulfonyl fluoroolefin ether monomer in the filtrate were recovered and reused using the recovery system.

[0103] Polymer data: via F 19NMR and IR analyses confirmed it to be a quaternary copolymer. The fluorine NMR integral value showed that the polymer structure contained 67.34% tetrafluoroethylene polymer units, 20.00% perfluorovinyl ether phosphonate polymer units, 5.32% perfluorovinyl phosphonate polymer units, and 7.34% perfluorosulfonyl fluoroolefin ether polymer units. The total ion exchange capacity of the resin was 1.37 mmol / g dry resin.

[0104] The GPC test showed a molecular weight of 230,000 and a molecular weight distribution value of 2.35.

[0105] IR spectrum: 1470cm -1 This is the absorption peak of the S=O vibration in sulfonyl fluoride; 1295 cm⁻¹ -1 The peak at 1030 cm⁻¹ represents the P=O vibration absorption peak in phosphonates; the peak at 1030 cm⁻¹ represents the COC bond absorption peak, and the peaks at 1234 and 1153 cm⁻¹ are also significant. -1 The two strongest absorptions are caused by CF vibrations; 986cm -1 Caused by -CF3 vibration; 722cm -1 640cm -1 This is caused by the absorption of the -CF2-CF2- vibration after the copolymerization of tetrafluoroethylene.

[0106] Example 5:

[0107] The reactor was cleaned and 5.0L of deionized water and 55g of nano-calcium carbonate were added. The stirring device was turned on, and the reactor was evacuated and purged with high-purity nitrogen three times. After testing and confirming that the oxygen content inside the reactor was below 1ppm, the reactor was evacuated again. Then, 175g of perfluorovinyl ether phosphonate monomer (CF2=CF-O-CF2CF2-P=O-(OCH2CH3)2), 225g of perfluorovinyl phosphonate monomer (CF2=CF-CF2CF2-P=O-(OCH2CH3)2), and 725g of perfluorovinyl ether sulfonyl fluoride monomer (CF2=CF-O-CF2CF2-SO2F) were added to the reactor through the liquid feed valve. Finally, tetrafluoroethylene monomer was added to the reactor until the pressure reached 4.2 ppm. The pressure was raised to 55℃, and 450g of a 10% ammonium persulfate aqueous solution was added using a metering pump to initiate the polymerization reaction. Tetrafluoroethylene monomer was continuously introduced to maintain the reaction pressure at 4.2MPa. After 2 hours of reaction, the initiator was stopped, and the reaction was allowed to continue for 15 minutes before the addition of tetrafluoroethylene monomer was stopped. The reactor was cooled using a cooling circulation system, and unreacted tetrafluoroethylene monomer was recovered using a recovery system. The milky white slurry in the reactor was discharged into a post-processing system through a discharge valve, filtered, and separated to obtain a white polymer powder. This powder was then dried in a 100℃ oven to obtain a polymeric phosphonic acid precursor polymer. The perfluorophosphonate monomer and perfluorosulfonyl fluoride monomer in the filtrate were recovered and reused using the recovery system.

[0108] Polymer data: via F 19 NMR and IR analyses confirmed it to be a quaternary copolymer. Fluorine NMR integral values ​​showed that the polymer structure contained 82.34% tetrafluoroethylene polymer units, 4.85% perfluorovinyl ether phosphonate polymer units, 3.14% perfluorovinyl phosphonate polymer units, and 9.67% perfluorosulfonyl fluoroene ether polymer units. The total ion exchange capacity of the resin was 0.92 mmol / g dry resin.

[0109] The GPC test showed a molecular weight of 358,000 and a molecular weight distribution value of 1.65.

[0110] IR spectrum: 1468cm -1 This is the absorption peak of the S=O vibration in sulfonyl fluoride; 1290 cm⁻¹ -1 The peak at 1030 cm⁻¹ represents the P=O vibration absorption peak in phosphonates; the peak at 1030 cm⁻¹ represents the COC bond absorption peak, and the peaks at 1230 and 1153 cm⁻¹ are also significant. -1 The two strongest absorptions are caused by CF vibrations, 720cm -1 640cm -1 This is caused by the absorption of the -CF2-CF2- vibration after the copolymerization of tetrafluoroethylene.

[0111] Comparative Example 1: A+D1

[0112] To compare the effect of introducing a copolymer structure with perfluorovinyl phosphate structural units on improving the thermal stability of perfluoro ionic polymers, the polymerization reaction conditions of Example 5 were used. Other factors such as temperature, pressure, and initiator remained unchanged, but only 275g of perfluorovinyl ether phosphonate monomer (CF2=CF-O-CF2CF(CF3)-O-CF2CF2-P=O-(OCH3)2) and 550g of perfluorovinyl ether sulfonyl fluoride monomer (CF2=CF-O-CF2CF2-SO2F) were added for polymerization. The same post-treatment processes as in Examples 1-6, including flocculation, separation, and drying, were then performed to obtain the resin precursor polymer.

[0113] Polymer data: via F 19 NMR and IR analyses confirmed it to be a terpolymer. The fluorine NMR integral value showed that the polymer structure contained 80.23% tetrafluoroethylene polymer units, 15.85% perfluorovinyl ether phosphonate polymer units, and 3.92% perfluorosulfonyl fluoroene ether polymer units. The total ion exchange capacity of the resin was 0.95 mmol / g dry resin.

[0114] The GPC test showed a molecular weight of 310,000 and a molecular weight distribution value of 1.49.

[0115] IR spectrum: 1468cm -1 This is the absorption peak of the S=O vibration in sulfonyl fluoride; 1217 cm⁻¹ -1 The peak at 1028 cm⁻¹ represents the P=O vibration absorption peak in phosphonates; the peak at 1230 and 1150 cm⁻¹ represents the COC bond absorption peak. -1 The two strongest absorptions are caused by CF vibrations, 720cm -1 640cm -1 This is caused by the absorption of the -CF2-CF2- vibration after the copolymerization of tetrafluoroethylene.

[0116] Comparative Example 2 A+B

[0117] To compare the effect of introducing a copolymer structure with a perfluorovinyl ether sulfonyl fluoride structural unit on the low-temperature conductivity of perfluoro ionic polymers, the polymerization reaction conditions of Example 3 were used. With other conditions such as temperature, pressure, and initiator unchanged, only 375g of perfluorovinyl ether phosphonate monomer (CF2=CF-O-CF2CF(CF3)-O-CF2CF2-P=O-(OCH3)2) and 250g of perfluorovinyl phosphonate monomer (CF2=CF-CF2-P=O-(OCH3)2) were added for polymerization. Subsequently, the same post-treatment processes as in Examples 1-6, such as flocculation separation and drying, were performed to obtain the resin precursor polymer.

[0118] Polymer data: via F 19 NMR and IR analyses confirmed it to be a terpolymer. The fluorine NMR integral value showed that the polymer structure contained 75.62% tetrafluoroethylene polymer units, 17.09% perfluorovinyl ether phosphonate polymer units, and 7.29% perfluorovinyl phosphonate polymer units. The total ion exchange capacity of the resin was 1.01 mmol / g dry resin.

[0119] The GPC test showed a molecular weight of 231,000 and a molecular weight distribution value of 1.27.

[0120] IR spectrum: 1295 cm⁻¹ -1 These are absorption peaks for the P=O vibration in phosphonates; 1238 and 1150 cm⁻¹ -1 The two strongest absorptions are caused by CF vibrations; the absorption peak at 1033 cm⁻¹ is for the POC ether bond, and the peak at 724 cm⁻¹ is for the ether bond. -1 642cm -1 This is caused by the absorption of the -CF2-CF2- vibration after the copolymerization of tetrafluoroethylene.

[0121] Application Example 1:

[0122] This application example illustrates the process of salt conversion and acidification of polymeric phosphonic acid precursor polymers.

[0123] The polymeric phosphonic acid precursor polymers obtained in Examples 1-5 were added to a transformation tank containing a 20% potassium hydroxide solution at a temperature of 70°C. After heating for 48 hours, the sulfonyl fluoride (-SO2F) side group was converted to potassium sulfonate (-SO3K), and the (-PO(OR)2) side group in the phosphonate ester was converted to potassium phosphite (-PO3K2).

[0124] After successful salt conversion, the resin was washed 8 times with pure water and then added to a nitric acid solution (HNO3) with a concentration of 15% by mass at a temperature of 60°C. The resin was left in the acid solution for 4 hours and the acid solution was replaced 4 times. Then, it was rinsed with deionized water at 50°C in a high-purity water bath for 4 hours. The sodium sulfonate (-SO3K) side group in the polymer was converted to the sulfonic acid ion (-SO3H) form, and the (-PO3K2) side group in the sodium phosphonite was converted to phosphorous acid (-PO3H2), thus obtaining a wide-temperature-range polymerized phosphonic acid resin (M1-M5).

[0125] The above operations were repeated on the resin precursor polymers obtained in Comparative Examples 1-2 to obtain resin polymers (D1-D2).

[0126] The tensile strength, resistivity, thermal decomposition temperature, and glass transition temperature of the resin polymer after salt conversion and acidification in Application Example 1 were tested.

[0127] The test method for tensile strength is GB / T1040-92.

[0128] The resistivity test method is as follows: a 25 μm thick film is obtained by melt extruding the resin polymer, and the film is tested using an electrochemical impedance spectroscopy instrument under the conditions of T=155℃, T=105℃ and T=25℃, 50%RH, respectively, with reference to the national standard GB / T 20042.3-2009 Proton Exchange Membrane Fuel Cell Part 3: Proton Exchange Membrane Test Methods.

[0129] The method for testing the thermal decomposition temperature is as follows: the temperature is obtained by testing the thermogravimetric curve using TG.

[0130] The glass transition temperature was determined using DMA testing.

[0131] The test samples were wide-temperature-range polymeric phosphonic acid resins (M1-M5) obtained after salt conversion and acidification in Application Example 1, and resin polymers (D1-D2) obtained after salt conversion and acidification.

[0132] The resin polymer D1 was tested and found to have a thermal decomposition temperature of 359°C and a resistivity at high temperature higher than that of the wide-temperature-range polymeric phosphonic acid resins (M1-M5); the resin polymer D2 had a resistivity as high as 102.04 Ω·cm at 25°C; the performance data of the wide-temperature-range polymeric phosphonic acid resins (M1-M5) are shown in Table 1.

[0133] Table 1. Properties of polymeric phosphonic acid resins over a wide temperature range

[0134]

[0135] As shown in Table 1, the thermal decomposition temperatures of M1-M5 were 365~395℃, which is significantly higher than that of D1. This is because the present invention not only uses perfluorovinyl ether phosphonate monomers, but also uses perfluorovinyl ether sulfonyl fluoride monomers and perfluorovinyl ether sulfonyl fluoride monomers in synergistic effect. By using perfluorovinyl phosphonate units, a fully C-bonded polymerization unit is introduced into the side chain, which improves the high-temperature thermal stability of the entire polymeric phosphonic acid resin.

[0136] At 25°C, the resistivity of M1-M5 is significantly lower than that of D2. This is because, within a certain range, the present invention employs the synergistic effect of perfluorovinyl ether phosphonic acid polymerization unit, perfluorovinyl phosphoric acid polymerization unit, and perfluoroene ether sulfonic acid polymerization unit to jointly reduce the resistivity of polymeric phosphonic acid resin at room temperature and broaden the temperature range of polymeric phosphonic acid resin.

[0137] Example 6:

[0138] Prepare a 2 kg mixture of water and n-propanol, wherein the water mass fraction is 30%. Add 410 g of the resin prepared in Example 1 to the above mixture, then transfer it to an autoclave, seal it, purge with nitrogen for stirring, heat to 180°C, keep it at that temperature for 4 hours, cool it to room temperature, remove the mixture, and separate it by carbon tetrachloride extraction at room temperature and pressure. Remove the lower layer solution to obtain a dispersion with a solid content of 22%.

[0139] Example 7:

[0140] Prepare a 2 kg mixture of water, isopropanol, and DMF (with a mass ratio of isopropanol to DMF of 2:1), wherein the water content is 36%. Add 400 g of the resin prepared in Example 1 to the above mixture, transfer it to an autoclave, seal it, and then stir under nitrogen protection. Heat the mixture to 220°C, keep it at that temperature for 5 hours, and then cool it to room temperature. Remove the mixture, and extract it using carbon tetrachloride at room temperature and pressure. Remove the lower layer solution to obtain a resin solution with a solid content of 20%.

[0141] Example 8:

[0142] Prepare a 2 kg mixture of water, ethanol, and ethylene glycol (ethanol to ethylene glycol in a 1:1 mass ratio), with water comprising 50% by mass. Add 590 g of the resin prepared in Example 1 to the mixture, transfer it to an autoclave, seal it, and then stir under nitrogen protection. Heat the mixture to 200°C, maintain the temperature for 4 hours, and then cool it to room temperature. Remove the mixture and separate it by carbon tetrachloride extraction at room temperature and pressure. The lower layer solution is then removed to obtain a dispersion with a solid content of 30%.

[0143] Example 9:

[0144] Prepare a 2 kg mixture of water, DMF, and cyclohexanone (DMF to cyclohexanone mass ratio of 5:1), with water comprising 32% by mass. Add 495 g of the resin prepared in Example 4 to the mixture, transfer to an autoclave, seal, and purge with nitrogen for stirring. Heat to 190°C, maintain the temperature for 6 hours, cool to room temperature, remove the mixture, and separate by carbon tetrachloride extraction at room temperature and pressure. Remove the lower layer solution to obtain a film-forming resin dispersion with a solid content of 25%.

[0145] Comparative Example 3

[0146] Prepare a 2 kg mixed solution of water and isopropanol, wherein the water mass fraction is 67%, and add 390 g of perfluorosulfonic acid resin with an exchange capacity of 1.1 mmol / g. The structure is as follows: Then, the mixture was transferred to an autoclave, sealed, and protected with nitrogen gas while stirring. It was heated to 280°C, kept at that temperature for 8 hours, and then cooled to room temperature. The mixed solution was then removed and separated by carbon tetrachloride extraction at room temperature and pressure. The lower layer solution was then removed, which yielded a resin solution with a solid content of 20% after stirring and dispersing.

[0147] Comparative Example 4

[0148] Prepare a 2 kg mixed solution of water and ethylene glycol, wherein the water mass fraction is 58%, and add 490 g of perfluorosulfonic acid resin with an exchange capacity of 1.2 mmol / g. The structure is as follows: Then, the mixture is transferred to an autoclave, sealed, and protected with nitrogen while stirring. It is then heated to 250°C, kept at that temperature for 10 hours, and cooled to room temperature. The mixed solution is then removed and separated by carbon tetrachloride extraction at room temperature and pressure. The lower layer solution is then removed to obtain a resin solution with a solid content of 30%.

[0149] Application Example 2

[0150] The dispersions prepared in Examples 6-9 and Comparative Examples 3 and 4 were coated onto films, and the solvent was heated to evaporate the films, resulting in 12 μm proton exchange membranes.

[0151] The prepared resin solution and proton exchange membrane were subjected to performance tests, and the performance data are shown in Table 2. The performance testing methods are as follows:

[0152] The solid content of the resin dispersion was measured using a halogen analyzer, and the micelle size was measured using a Brookhaven particle size analyzer. Smaller ionomer micelle sizes in the resin dispersion result in more uniform catalyst dispersion and higher proton conductivity of the catalyst layer.

[0153] Table 1. Resin solution performance data for Examples 6-9 and Comparative Examples 3 and 4

[0154]

Claims

1. A wide-temperature-range polymeric phosphonic acid resin dispersion, characterized in that, Including wide-temperature-range polymeric phosphonic acid resins and organic solvents; The wide-temperature-range polymeric phosphonic acid resin is composed of fluorinated olefin units, perfluorovinyl ether phosphonic acid units, perfluorovinyl phosphoric acid units, and perfluoroolefin ether sulfonic acid units; The structural formula of the wide-temperature-range polymeric phosphonic acid resin is as follows: ； In the formula, k is an integer from 0 to 3, f is an integer from 1 to 4; g is an integer from 0 to 4; t is an integer from 0 to 3, v is an integer from 1 to 4; a, b and c are integers from 1 to 20, and a', b' and c' are integers from 1 to 3. In the formula, R is —(OCF2) m (CF2) n X, where X is either Cl or F; m and n are integers from 0 to 3; x, y, and z satisfy the following conditions: x / (x+y+z)=0.1-0.5, y / (x+y+z)=0.1-0.5, z / (x+y+z)=0.1-0.

6.

2. The wide-temperature-range polymeric phosphonic acid resin dispersion according to claim 1, characterized in that, The organic solvent is one or more of n-propanol, isopropanol, methanol, acetone, N,N-dimethylformamide (DMF), methylamide, ethylene glycol, and cyclohexanone.

3. The wide-temperature-range polymeric phosphonic acid resin dispersion according to claim 1, characterized in that, In the wide-temperature-range polymeric phosphonic acid resin dispersion, the mass percentage of the wide-temperature-range polymeric phosphonic acid resin is 2.5wt%-50wt%, the mass percentage of pure water is 10wt%-95wt%, and the mass percentage of organic solvent is 2.5wt%-87.5wt%.

4. The wide-temperature-range polymeric phosphonic acid resin dispersion according to claim 3, characterized in that, In the wide-temperature-range polymeric phosphonic acid resin dispersion, the mass percentage of the wide-temperature-range polymeric phosphonic acid resin is 5wt%-40wt%, the mass percentage of pure water is 15wt%-75wt%, and the mass percentage of organic solvent is 5wt%-75wt%.

5. The wide-temperature-range polymeric phosphonic acid resin dispersion according to claim 1, characterized in that, The micelle size of the wide-temperature-range polymeric phosphonic acid resin dispersion is 100-400 nm.

6. The method for preparing a wide-temperature-range polymeric phosphonic acid resin dispersion as described in any one of claims 1-5, characterized in that, The specific operating steps are as follows: S1: Add the above-mentioned wide-temperature-range polymeric phosphonic acid resin, pure water, and organic solvent into the autoclave; S2: Under inert gas protection, mechanically stir and dissolve at high temperature. Then stop heating and stirring, and cool to room temperature to obtain a mixed solution. S3: After liquid-liquid separation, the mixed solution obtained in step S2 is used to obtain a wide-temperature-range polymeric phosphonic acid resin dispersion.

7. The method for preparing a wide-temperature-range polymeric phosphonic acid resin dispersion according to claim 6, characterized in that, In step S2, the inert gas is selected from nitrogen, argon, or xenon. The temperature of the mechanical stirring is 120℃~280℃; The stirring pressure is 1MPa-5MPa; The mechanical stirring time is 2 to 20 hours.

8. The method for preparing a wide-temperature-range polymeric phosphonic acid resin dispersion according to claim 7, characterized in that, In step S2, the temperature of the mechanical stirring is 140℃~260℃; The stirring pressure is 2MPa-4MPa; The mechanical stirring time is 4 to 15 hours.

9. The method for preparing a wide-temperature-range polymeric phosphonic acid resin dispersion according to claim 6, characterized in that, In step S3, the liquid-liquid separation method includes distillation and extraction separation; The extraction and separation method is as follows: the mixed solution is transferred to a separatory funnel, and after extraction and separation by carbon tetrachloride at room temperature and pressure, the lower layer solution is taken out to obtain a wide-temperature-range polymeric phosphonic acid resin dispersion.

10. The application of the wide-temperature-range polymeric phosphonic acid resin dispersion as described in any one of claims 1-5 or the wide-temperature-range polymeric phosphonic acid resin dispersion prepared by the preparation method described in any one of claims 6-9 in the manufacture of fuel cells and electrolytic systems.

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