An ionic polymer, a method for preparing the same, and an application thereof

Abstract

The present application relates to the technical field of ion exchange membrane, and more particularly to a novel ion polymer, a preparation method and application thereof.The present application provides a novel ion polymer, which has a structure shown in formula I or formula II; wherein A is an aromatic unit; B is a rigid twisted structure unit; Q is an electron-withdrawing group; a is greater than or equal to 10; and b is any integer greater than or equal to 2.The introduction of a new acetal monomer constructs a flexible novel main chain of the polymer, and solves the contradiction between the performance balance of ion exchange membrane material, i.e., conductivity, stability and mechanical properties; formula I; formula II.

Description

Technical Field

[0001] This invention relates to the field of ion exchange membrane technology, and in particular to a novel ion polymer, its preparation method, and its application. Background Technology

[0002] Ion exchange membranes, as core components of next-generation electrochemical energy conversion systems, have attracted widespread attention in recent years due to their unique advantages in fields such as flow batteries, fuel cells, water electrolysis for hydrogen production, and electrochemical reduction of carbon dioxide. Developing ion exchange membranes with good chemical stability, high ion conductivity, and robust mechanical properties is considered a key challenge in the development of next-generation electrochemical energy technologies.

[0003] To obtain high-performance ion exchange membranes, researchers have made significant efforts to control the polymer backbone. For example, they have investigated different main chain structures (including polyolefins, polystyrene, polyethersulfone, and polyetherketone) and ionic groups (pyrazoles, imidazoles, metal-coordinated cations, etc.). These materials often exhibit numerous instabilities under alkaline conditions. For instance, the degradation of polyaryl ether backbones and the degradation of nitrogen-containing cations under alkaline conditions often occur through nucleophilic substitution and Hoffmann degradation pathways. Therefore, researchers have developed a new generation of polymers with ether-free and piperidinone backbone structures as alkali-resistant anion exchange membrane materials.

[0004] However, the practical application of ion exchange membranes (AEMs) remains limited by the contradiction between ionic conductivity and mechanical stability under alkaline conditions: high ionic conductivity requires a high density of cationic groups (such as quaternary ammonium salts), but under strongly alkaline conditions, this makes AEMs susceptible to nucleophilic attack, leading to membrane degradation. Furthermore, higher ionic conductivity results in higher water absorption and greater dimensional expansion, which in turn leads to a decrease in the mechanical strength of AEMs. Insufficient mechanical strength, dimensional swelling, and gas cross-contamination further restrict their large-scale application. Addressing these challenges, how to precisely and effectively control the polymer structure and overcome the contradiction between ionic conductivity, chemical stability, and mechanical properties remains a challenging research problem. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a novel ion exchange polymer, its preparation method and application, which constructs a flexible novel polymer backbone by introducing a new acetal monomer, thereby resolving the contradiction of balancing the "conduction-stability-mechanical" properties of ion exchange membrane materials.

[0006] This invention provides a novel ionic polymer having the structure shown in Formula I or Formula II;

[0007] Formula I; Formula II;

[0008] Where A is an aromatic unit; B is a rigid twisted structural unit; Q is an electron-withdrawing group, including but not limited to nitrogen-containing groups; a ≥ 10; b is any integer greater than or equal to 2.

[0009] Preferably, for the structure shown in Equation II, when b=2, its structure is as shown in Equation (1); when b=3, its structure is as shown in Equation (2); when b=4, its structure is as shown in Equation (3); as the value of b continues to increase, the corresponding structures are deduced in the same way.

[0010] .

[0011] Preferably, the electron-withdrawing group Q is one or more of the following groups;

[0012] ;

[0013] Wherein, R2 is one or more of hydrogen, C1-C10 alkyl, C1-C10 substituted alkyl, C6-C100 aromatic or C6-C100 substituted aromatic; the substituents in the substituted alkyl and substituted aromatic are each independently selected from halogens.

[0014] This invention also provides a method for preparing the novel ionic polymer described above, comprising the following steps:

[0015] S1. Condensation reaction: Acetal monomer D and aromatic monomer A' are dispersed in dichloromethane, then mixed with a catalyst and stirred until the viscosity of the reaction solution increases to the point where it cannot be stirred by a magnetic stirrer. After washing and drying, the polymer precursor is obtained.

[0016] Alternatively, acetal monomer D, aromatic monomer A', and rigid twisted monomer B' can be dispersed in dichloromethane, then mixed with a catalyst, stirred, and reacted until the viscosity of the reaction solution increases to the point where it cannot be stirred with a magnetic stirrer. After washing and drying, the polymer precursor is obtained.

[0017] S2, Quaternization reaction: The polymer precursor is mixed with dimethyl sulfoxide solvent, the resulting mixed solution is mixed with a halogenated compound, and the reaction is stirred under light-protected conditions. After the reaction is completed, the mixture is washed and dried to obtain a novel ionic polymer.

[0018] Alternatively, the polymer precursor can be mixed with dimethyl sulfoxide solvent, and the resulting mixed solution can be mixed with a halogenated compound and a base. The mixture can be stirred and reacted under light-protected conditions. After the reaction is complete, the mixture can be washed and dried to obtain a novel ionic polymer.

[0019] Preferably, the aromatic monomer A' is one or more of the following compounds;

[0020]

[0021]

[0022] .

[0023] Preferably, the rigid torsion monomer B' is one or more of the following compounds;

[0024]

[0025] ;

[0026] Wherein, R1 is selected from one or more of hydrogen, C1-C10 alkyl, C1-C10 substituted alkyl, C6-C100 aromatic and C6-C100 substituted aromatic; the substituents in the substituted alkyl and substituted aromatic are each independently selected from halogens.

[0027] Preferably, the acetal monomer D has the structure shown in Formula III;

[0028] Formula III;

[0029] Where Q is an electron-withdrawing group;

[0030] R3 is selected from one or more of C1-C10 alkyl groups, C1-C10 substituted alkyl groups, C6-C100 aromatic groups, and C6-C100 substituted aromatic groups; the substituents in the substituted alkyl groups and substituted aromatic groups are each independently selected from halogens;

[0031] The catalyst is at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, and perfluorosulfonic acid resin.

[0032] The halogenated compound is at least one selected from monoiodoalkyl, monobromoalkyl, 2-bromoethylamine, 2-bromoethanol, ethyl 2-chloromethacrylate, 4-vinylbenzyl chloride, 1-(chloromethyl)-4-ethynylbenzene, 1-azido-4-(chloromethyl)benzene, 2-(chloromethyl), (5-bromopentyl)trimethylammonium bromide, and ethylene oxide.

[0033] The present invention also provides a novel crosslinked ionic polymer, which is prepared by reacting an ionic polymer with a crosslinking agent; the ionic polymer is the novel ionic polymer described above, or a novel ionic polymer prepared by the preparation method described above.

[0034] The present invention also provides a novel ion exchange membrane, which is prepared from the novel ion polymer described above, or the novel ion polymer prepared by the preparation method described above, or the cross-linked novel ion polymer described above.

[0035] This invention also provides an application of the novel ion exchange membrane described above in flow batteries, hydrogen production by water electrolysis, fuel cells, electrochemical ammonia synthesis, carbon dioxide reduction, salinity gradient energy conversion, electrodialysis, lithium extraction from salt lakes, or wastewater treatment.

[0036] This invention aims to enhance the flexibility of polymers by introducing flexible tertiary carbon spacer groups into the polymer backbone through the underlying design of monomer molecules and the use of acetal monomers. The developed novel polymers and their polymer films achieve a balance in the contradiction between "conduction-stability-mechanical" properties.

[0037] Furthermore, this invention reduces the amount of trifluoromethanesulfonic acid used in the synthesis process, and the method is simple, efficient, green, and environmentally friendly. Attached Figure Description

[0038] Figure 1 For the PTP-DMA of Embodiment 1 of the present invention 1 H NMR spectrum;

[0039] Figure 2 This is an appearance diagram of the anion exchange membrane PTP-DMA-Cl of Example 1 of the present invention;

[0040] Figure 3 This is a chloride ion conductivity curve of the anion exchange membrane PTP-DMA-Cl in Example 1 of the present invention;

[0041] Figure 4 The graph shows the resistance test results of the PTP-DMA polymer film in the TEMPTMA / MV aqueous flow battery of Example 1 of the present invention.

[0042] Figure 5 The graph shows the power performance test results of the PTP-DMA polymer membrane in a TEMPTMA / MV aqueous flow battery according to Example 1 of the present invention.

[0043] Figure 6 The graph shows the battery rate test results of the PTP-DMA polymer membrane in the TEMPTMA / MV aqueous flow battery of Example 1 of the present invention.

[0044] Figure 7 The graph shows the cycling performance of the PTP-DMA polymer membrane in a TEMPTMA / MV aqueous flow battery according to Example 1 of the present invention. Detailed Implementation

[0045] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0046] This invention provides a novel ionic polymer having the structure shown in Formula I or Formula II;

[0047] Formula I; Formula II;

[0048] Where A is an aromatic unit; B is a rigid twisted structural unit; Q is an electron-withdrawing group, including but not limited to nitrogen-containing groups; a ≥ 10; b is any integer greater than or equal to 2.

[0049] For the structure shown in Equation II, when b=2, its structure is as shown in Equation (1); when b=3, its structure is as shown in Equation (2); when b=4, its structure is as shown in Equation (3); as the value of b continues to increase, the corresponding structure follows the same pattern.

[0050] .

[0051] In some embodiments of the present invention, the aromatic unit A is one or more of the following groups (i.e., aromatic monomer A');

[0052]

[0053]

[0054] .

[0055] In some embodiments of the present invention, the rigid twisted structural unit B is one or more of the groups corresponding to the following compounds (i.e., rigid twisted monomer B');

[0056]

[0057] ;

[0058] Wherein, R1 is selected from one or more of hydrogen, C1-C10 alkyl, C1-C10 substituted alkyl, C6-C100 aromatic and C6-C100 substituted aromatic; the substituents in the substituted alkyl and substituted aromatic are each independently selected from halogens.

[0059] In some embodiments of the present invention, the electron-withdrawing group Q is one or more of the following groups;

[0060] ;

[0061] Wherein, R2 is one or more of hydrogen, C1-C10 alkyl, C1-C10 substituted alkyl, C6-C100 aromatic or C6-C100 substituted aromatic; the substituents in the substituted alkyl and substituted aromatic are each independently selected from halogens.

[0062] In some embodiments of the present invention, the novel ionic polymer has the structure shown in formula (1);

[0063] ;

[0064] In equation (1), n ​​≥ 1.

[0065] This invention also provides a method for preparing the novel ionic polymer described above, comprising the following steps:

[0066] S1. Condensation reaction: Acetal monomer D and aromatic monomer A' are dispersed in dichloromethane, then mixed with a catalyst and stirred until the viscosity of the reaction solution increases to the point where it cannot be stirred by a magnetic stirrer. After washing and drying, the polymer precursor is obtained.

[0067] or

[0068] Acetal monomer D, aromatic monomer A' and rigid twisted monomer B' were dispersed in dichloromethane, then mixed with a catalyst and stirred until the viscosity of the reaction solution increased to the point that it could not be stirred with a magnetic stirrer. After washing and drying, the polymer precursor was obtained.

[0069] S2, Quaternization reaction: The polymer precursor is mixed with dimethyl sulfoxide solvent, the resulting mixed solution is mixed with a halogenated compound, and the reaction is stirred under light-protected conditions. After the reaction is completed, the mixture is washed and dried to obtain a novel ionic polymer.

[0070] Alternatively, the polymer precursor can be mixed with dimethyl sulfoxide solvent, and the resulting mixed solution can be mixed with a halogenated compound and a base. The mixture can be stirred and reacted under light-protected conditions. After the reaction is complete, the mixture can be washed and dried to obtain a novel ionic polymer.

[0071] Regarding step S1:

[0072] First scenario:

[0073] Acetal monomer D and aromatic monomer A' were dispersed in dichloromethane, then mixed with a catalyst and stirred until the viscosity of the reaction solution increased to the point where it could no longer be stirred with a magnetic stirrer. After washing and drying, the polymer precursor was obtained.

[0074] In some embodiments of the present invention, acetal monomer D and aromatic monomer A' are dispersed in dichloromethane and then mixed with a catalyst, specifically:

[0075] Acetal monomer D and aromatic monomer A' are dissolved in dichloromethane and stirred until homogeneous. Then, the catalyst is added dropwise. The stirring and mixing temperature is 0°C, and the time is 0.5~72 h, for example, 0.5 h. The dropwise addition time is 1.5~2.5 h, for example, 2 h.

[0076] In some embodiments of the present invention, the molar ratio of the aromatic monomer A' to the acetal monomer D is 1:1 to 3, for example, 1:1.

[0077] In some embodiments of the present invention, the molar ratio of the sum of the acetal monomer D and the aromatic monomer A' to the catalyst is 1:0.1 to 10, for example, 1:3.2.

[0078] The second scenario:

[0079] Acetal monomer D, aromatic monomer A', and rigid twisted monomer B' were dispersed in dichloromethane, then mixed with a catalyst and stirred until the viscosity of the reaction solution increased to the point where it could no longer be stirred with a magnetic stirrer. After washing and drying, the polymer precursor was obtained.

[0080] In some embodiments of the present invention, the total amount of the aromatic monomer A' and the rigid twisted monomer B' is in a molar ratio of 1:1 to 3 to the acetal monomer D.

[0081] In some embodiments of the present invention, the molar ratio of the sum of the acetal monomer D, the aromatic monomer A' and the rigid twisted monomer B' to the catalyst is 1:0.1~10.

[0082] In the first and second cases:

[0083] In some embodiments of the present invention, the acetal monomer D has the structure shown in Formula III;

[0084] Formula III;

[0085] Where Q is the same as above, and is an electron-withdrawing group, including but not limited to nitrogen-containing groups;

[0086] R3 is selected from one or more of C1-C10 alkyl groups, C1-C10 substituted alkyl groups, C6-C100 aromatic groups, and C6-C100 substituted aromatic groups; the substituents in the substituted alkyl groups and substituted aromatic groups are each independently selected from halogens.

[0087] In some embodiments of the present invention, the catalyst is at least one selected from trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, and perfluorosulfonic acid resin.

[0088] In some embodiments of the present invention, the temperature of the stirring reaction is -20 to 80°C, for example, 0°C; and the time is 1 hour to 7 days, for example, 24 hours.

[0089] In some embodiments of the present invention, the washing process uses water, specifically pure water.

[0090] In some embodiments of the present invention, the drying is vacuum drying.

[0091] Regarding step S2:

[0092] Quaternization reaction: The polymer precursor is mixed with dimethyl sulfoxide solvent, the resulting mixed solution is mixed with a halogenated compound, and the reaction is stirred under light-protected conditions. After the reaction is completed, the mixture is washed and dried to obtain a novel ionic polymer.

[0093] Alternatively, the polymer precursor can be mixed with dimethyl sulfoxide solvent, and the resulting mixed solution can be mixed with a halogenated compound and a base. The mixture can be stirred and reacted under light-protected conditions. After the reaction is complete, the mixture can be washed and dried to obtain a novel ionic polymer.

[0094] In some embodiments of the present invention, the halogenated compound is at least one selected from monoiodoalkyl, monobromoalkyl, 2-bromoethylamine, 2-bromoethanol, ethyl 2-chloromethacrylate, 4-vinylbenzyl chloride, 1-(chloromethyl)-4-ethynylbenzene, 1-azido-4-(chloromethyl)benzene, 2-(chloromethyl), (5-bromopentyl)trimethylammonium bromide, and ethylene oxide.

[0095] In some embodiments of the present invention, the base may be at least one of inorganic bases and / or organic bases; specifically, it may be at least one of sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, trimethylamine, triethylamine, N,N-dimethylethylenediamine, and N,N-diisopropylethylamine.

[0096] In some embodiments of the present invention, the molar ratio of the polymer precursor, the halogenated compound and the base is 1:0.5~20:0~50, for example 1:0.5~2:0.5~2, specifically 1:1:1.

[0097] In some embodiments of the present invention, the temperature of the stirring reaction is 0~160°C, for example 25°C; and the time is 1h~3d, for example 24h.

[0098] In some embodiments of the present invention, the washing process uses acetone and water in sequence, and the water can be pure water.

[0099] In some embodiments of the present invention, the drying is vacuum drying.

[0100] The polymer precursor prepared in the first case described above undergoes a reaction in step S2 to finally obtain a novel ionic polymer with the structure shown in Formula I.

[0101] The polymer precursor prepared in the second case described above undergoes a reaction in step S2 to finally obtain a novel ionic polymer with the structure shown in Formula II.

[0102] The novel ionic polymer is an anionic polymer.

[0103] The present invention also provides a novel crosslinked ionic polymer, which is prepared by reacting an ionic polymer with a crosslinking agent; the ionic polymer is the novel ionic polymer described above, or a novel ionic polymer prepared by the preparation method described above.

[0104] In some embodiments of the present invention, the crosslinking agent is one or more of the following structural formulas;

[0105]

[0106] Wherein, X is F, Cl, Br or I; R4 is selected from one or more of hydrogen, C1-C10 alkyl, C1-C10 substituted alkyl, C6-C100 aromatic and C6-C100 substituted aromatic; the substituents in the substituted alkyl and substituted aromatic are each independently selected from halogens.

[0107] In some embodiments of the present invention, the reaction between the ionic polymer and the crosslinking agent is carried out in the presence of a base. The base may be at least one of inorganic and / or organic bases; specifically, it may be at least one of sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, trimethylamine, triethylamine, N,N-dimethylethylenediamine, and N,N-diisopropylethylamine.

[0108] In some embodiments of the present invention, the reaction temperature of the ionomer and the crosslinking agent is 0~50°C and the reaction time is 0.5~72 h.

[0109] The present invention also provides a novel ion exchange membrane, which is prepared from the novel ion polymer described above, or the novel ion polymer prepared by the preparation method described above, or the cross-linked novel ion polymer described above.

[0110] The novel ion exchange membrane is an anion exchange membrane or a cation exchange membrane.

[0111] This invention also provides a method for preparing the novel ion exchange membrane described above, comprising the following steps:

[0112] The ion polymer is dissolved in an organic solvent to obtain a casting solution. The casting solution is then cast and dried to obtain a novel ion exchange membrane.

[0113] The ionic polymer is the novel ionic polymer described above, or the novel ionic polymer prepared by the preparation method described above, or the cross-linked novel ionic polymer described above.

[0114] In some embodiments of the present invention, the organic solvent includes, but is not limited to, dichloromethane, trichloromethane, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, alcohols, or n-hexane.

[0115] In some embodiments of the present invention, the mass-to-volume ratio of the ionic polymer to the organic solvent is 0.1-100 g: 0.1-99.9 mL, for example, 0.1 g: 20 mL.

[0116] In some embodiments of the present invention, the method for casting the casting solution is as follows: the casting solution is uniformly coated on a glass plate.

[0117] In some embodiments of the present invention, the drying method is oven drying, specifically, the oven drying temperature is 30~120℃, for example 60℃; the drying time is 5~24 h, for example 8 h.

[0118] In some embodiments of the present invention, after drying, the process further includes immersing the dried ion exchange membrane in an aqueous sodium chloride solution. The concentration of the aqueous sodium chloride solution is 0.8~5 mol / L, for example, 1 mol / L. The immersion time is 24~72 h, for example, 24 h. Immersion in the NaCl aqueous solution is to change the counterions, activate the ion exchange membrane, and enable it to have battery performance. The present invention does not have any special limitations on the type of counterions, nor is it limited to using an aqueous sodium chloride solution.

[0119] In some embodiments of the present invention, the thickness of the novel ion exchange membrane is 10~100 μm, for example 60 μm.

[0120] The present invention also provides an application of the novel ion exchange membrane described above, or the novel ion exchange membrane prepared by the method described above, in flow batteries, hydrogen production by water electrolysis, fuel cells, electrochemical ammonia synthesis, carbon dioxide reduction, salinity gradient energy conversion, electrodialysis, lithium extraction from salt lakes, or wastewater treatment.

[0121] This invention provides a novel ion-exchange polymer and a method for preparing a novel ion-exchange membrane. By introducing a novel acetal monomer to construct a flexible new polymer backbone, the contradiction in balancing the "conduction-stability-mechanical" properties of ion-exchange membrane materials is resolved. The ion-exchange polymer prepared by this invention starts with the design of the monomer molecule, introducing intercalating tertiary carbons into the all-carbon backbone of the acetal monomer. This improves the mechanical strength of the ion-exchange membrane by increasing the flexibility of the polymer molecular chain, and reduces the amount of trifluoromethanesulfonic acid used in the synthesis process. This method is simple, efficient, green, and environmentally friendly.

[0122] The present invention does not impose any special restrictions on the source of the raw materials used above, and they can be commercially available.

[0123] To further illustrate the present invention, the following detailed description of a novel ionic polymer, its preparation method, and its application, in conjunction with embodiments, is provided by the present invention, but should not be construed as limiting the scope of protection of the present invention.

[0124] Example 1

[0125] 1. Dissolve 1.61 g (10 mmol) of dimethylaminoacetaldehyde diethanol (CAS No.: 3616-56-6) and 2.30 g (10 mmol) of p-terphenyl (CAS No.: 92-94-4) in 50 mL of dichloromethane and stir at 0 °C for 30 min; then add 5 mL (56.67 mmol) of trifluoromethanesulfonic acid and 0.5 mL (6.58 mmol) of trifluoroacetic acid dropwise over a period of 2 h; then stir the reaction mixture at 0 °C for 24 h until the viscosity of the reaction solution increases to the point where it cannot be stirred with a magnetic stirrer. Wash with pure water and vacuum dry to obtain a pale yellow powder, which is the polymer precursor.

[0126] 2. Dissolve 10 mmol of the pale yellow powder in 50 mL of dimethyl sulfoxide; add 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate, and stir the mixture at 25 °C in the dark for 24 h; then wash with acetone and pure water in sequence, and dry under vacuum to obtain the pale yellow powder, which is the novel anionic polymer PTP-DMA.

[0127] Analysis of PTP-DMA 1 H NMR spectrum, results as follows Figure 1 As shown. Figure 1 For the PTP-DMA of Embodiment 1 of the present invention 1 H NMR spectrum. From Figure 1 It can be seen that the PTP-DMA has the structure shown in equation (1).

[0128] 3. Dissolve 100 mg of the novel anionic polymer PTP-DMA in 20 mL of dimethyl sulfoxide to prepare a PTP-DMA solution. Then, uniformly coat the PTP-DMA solution onto a glass plate and bake at 60 °C for 8 h to obtain a PTP-DMA membrane. Immerse the PTP-DMA membrane in a 1 mol / L sodium chloride aqueous solution for 24 h to obtain a counterion of Cl. - The anion exchange membrane PTP-DMA-Cl has a thickness of 60 μm.

[0129] Its appearance is shown in the figure. Figure 2 As shown. Figure 2 This is an appearance diagram of the anion exchange membrane PTP-DMA-Cl of Embodiment 1 of the present invention.

[0130] Cl of the obtained PTP-DMA-Cl film - The ionic conductivity was detected using the four-electrode AC impedance method, and the chloride ion conductivity curve was obtained, as shown in the figure. Figure 3 As shown. Figure 3 This is a chloride ion conductivity curve of the PTP-DMA-Cl anion exchange membrane from Example 1 of the present invention. Figure 3 It can be seen that the chloride ion conductivity of the PTP-DMA-Cl membrane at 30~80℃ is 15~52 mScm. -1 .

[0131] The PTP-DMA polymer membrane obtained in Example 1 was applied to a TEMPTMA / MV aqueous flow battery. The positive electrode electrolyte was a 5 mL mixed aqueous solution of TEMPTMA and NaCl (wherein the concentration of TEMPTMA was 1.5 mol / L and the concentration of NaCl was 0.5 mol / L), and the negative electrode electrolyte was a 10 mL mixed aqueous solution of MV and NaCl (wherein the concentration of MV was 1.1 mol / L and the concentration of NaCl was 0.5 mol / L). The membrane resistance was measured as follows: Figure 4 As shown, Figure 4 This is a graph showing the resistance test results of the PTP-DMA polymer film in a TEMPTMA / MV aqueous flow battery according to Example 1 of the present invention. Figure 4 It can be seen that the film resistance is 1.086 Ω cm. 2 The corresponding maximum battery power is as follows: Figure 5 As shown. Figure 5 This is a graph showing the power performance test results of the PTP-DMA polymer membrane in a TEMPTMA / MV aqueous flow battery according to Example 1 of the present invention. Figure 5 It can be seen that the maximum battery power is 359.7 mW / cm². -2 . Figure 6This is a graph showing the rate test results of the PTP-DMA polymer membrane in a TEMPTMA / MV aqueous flow battery according to Example 1 of the present invention. Figure 6 It can be seen that the battery has excellent rate performance, and the battery operates at a current density of 200 mA cm⁻¹. -2 The capacity utilization rate is 92%, and the energy efficiency is 71.7%. Figure 7 This is a graph showing the cycling performance of the PTP-DMA polymer membrane in a TEMPTMA / MV aqueous flow battery according to Example 1 of the present invention. Figure 7 It can be seen that the battery operates at 200mA cm -2 It can stably cycle for 800 times.

[0132] Example 2

[0133] 1. Dissolve 1.191 g (10 mmol) of methylaminoacetaldehyde dimethyl acetal (CAS No.: 122-07-6) and 2.30 g (10 mmol) of p-terphenyl (CAS No.: 92-94-4) in 50 mL of dichloromethane and stir at 0 °C for 30 min; then add 5 mL (56.67 mmol) of trifluoromethanesulfonic acid and 0.5 mL (6.58 mmol) of trifluoroacetic acid dropwise over a period of 2 h; then stir the reaction mixture at 0 °C for 24 h until the viscosity of the reaction solution increases to the point where it cannot be stirred with a magnetic stirrer. Wash with pure water and vacuum dry to obtain a pale yellow powder, which is the polymer precursor.

[0134] 2. Dissolve 10 mmol of the pale yellow powder in 50 mL of dimethyl sulfoxide; add 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate, and stir the mixture at 25 °C in the dark for 24 h; then wash with acetone and pure water in sequence, and dry under vacuum to obtain the pale yellow powder, which is the novel anionic polymer PTP-DMB.

[0135] 3. Prepare a PTP-DMB solution by dissolving 100 mg of the novel anionic polymer PTP-DMB in 20 mL of N-methylpyrrolidone. Then, uniformly coat the PTP-DMB solution onto a glass plate and bake at 60 °C for 8 hours to obtain a PTP-DMB membrane. Immerse the PTP-DMB membrane in a 1 mol / L sodium chloride aqueous solution for 24 hours to obtain a counterion of Cl-. - The anion exchange membrane PTP-DMB-Cl has a thickness of 60 μm.

[0136] Example 3

[0137] 1. Dissolve 1.61 g (10 mmol) of dimethylaminoacetaldehyde diethanol (CAS No.: 3616-56-6) and 1.54 g (10 mmol) of biphenyl (CAS No.: 92-52-4) in 50 mL of dichloromethane and stir at 0 °C for 30 min; then add 5 mL (56.67 mmol) of trifluoromethanesulfonic acid and 0.5 mL (6.58 mmol) of trifluoroacetic acid dropwise over a period of 2 h; then stir the reaction mixture at 0 °C for 24 h until the viscosity of the reaction solution increases to the point where it cannot be stirred with a magnetic stirrer. Wash with pure water and vacuum dry to obtain a pale yellow powder, which is the polymer precursor.

[0138] 2. Dissolve 10 mmol of the pale yellow powder in 50 mL of dimethyl sulfoxide; add 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate, and stir the mixture at 25 °C in the dark for 24 h; then wash with acetone and pure water in sequence, and dry under vacuum to obtain the pale yellow powder, which is the novel anionic polymer BP-DMA.

[0139] 3. Prepare a BP-DMA solution by dissolving 100 mg of the novel anionic polymer BP-DMA in 20 mL of N-methylpyrrolidone. Then, uniformly coat the BP-DMA solution onto a glass plate and bake at 60 °C for 8 hours to obtain a BP-DMA membrane. Immerse the BP-DMA membrane in a 1 mol / L sodium chloride aqueous solution for 24 hours to obtain a counterion of Cl-. - The anion exchange membrane BP-DMA-Cl has a thickness of 60 μm.

[0140] Example 4

[0141] 1. Dissolve 1.191 g (10 mmol) of methylaminoacetaldehyde dimethyl acetal (CAS No.: 122-07-6) and 1.54 g (10 mmol) of biphenyl (CAS No.: 92-52-4) in 50 mL of dichloromethane and stir at 0 °C for 30 min; then add 5 mL (56.67 mmol) of trifluoromethanesulfonic acid and 0.5 mL (6.58 mmol) of trifluoroacetic acid dropwise over a period of 2 h; then stir the reaction mixture at 0 °C for 24 h until the viscosity of the reaction solution increases to the point where it cannot be stirred with a magnetic stirrer. Wash with pure water and vacuum dry to obtain a pale yellow powder, which is the polymer precursor.

[0142] 2. Dissolve 10 mmol of the pale yellow powder in 50 mL of dimethyl sulfoxide; add 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate, and stir the mixture at 25 °C in the dark for 24 h; then wash with acetone and pure water in sequence, and dry under vacuum to obtain the pale yellow powder, which is the novel anionic polymer BP-DMB.

[0143] 3. Prepare a BP-DMB solution by dissolving 100 mg of the novel anionic polymer BP-DMB in 20 mL of N-methylpyrrolidone. Then, uniformly coat the BP-DMB solution onto a glass plate and bake at 60 °C for 8 hours to obtain a BP-DMB membrane. Immerse the BP-DMB membrane in a 1 mol / L sodium chloride aqueous solution for 24 hours to obtain a counterion of Cl-. - The anion exchange membrane BP-DMB-Cl has a thickness of 60 μm.

[0144] Example 5

[0145] 1. Dissolve 1.62 g (10 mmol) of 3,3-diethoxypropionic acid (CAS No.: 6191-97-5) and 1.54 g (10 mmol) of biphenyl (CAS No.: 92-52-4) in 50 mL of dichloromethane and stir at 0 °C for 30 min; then add 5 mL (56.67 mmol) of trifluoromethanesulfonic acid and 0.5 mL (6.58 mmol) of trifluoroacetic acid dropwise over a period of 2 h; then stir the reaction mixture at 0 °C for 24 h until the viscosity of the reaction solution increases to the point where it cannot be stirred with a magnetic stirrer. Wash with pure water and vacuum dry to obtain a pale yellow powder, which is the polymer precursor.

[0146] 2. Dissolve 10 mmol of the pale yellow powder in 50 mL of dimethyl sulfoxide; add 1.42 g (10 mmol) of iodomethane and 1.382 g (10 mmol) of potassium carbonate, and stir the mixture at 25 °C in the dark for 24 h; then wash with acetone and pure water in sequence, and dry under vacuum to obtain the pale yellow powder, which is the novel cationic polymer BP-DMC.

[0147] 3. Dissolve 100 mg of the novel cationic polymer BP-DMC in 20 mL of DMSO to prepare a BP-DMC solution. Then, uniformly coat the BP-DMC solution onto a glass plate and bake at 60 °C for 8 h to obtain a BP-DMC membrane. Immerse the BP-DMC membrane in a 1 mol / L sodium chloride aqueous solution for 24 h to obtain a counterion of Cl. - The anion exchange membrane BP-DMC-Cl has a thickness of 60 μm.

[0148] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. An ionomer, characterized in that, By introducing spacer tertiary carbons into the full carbon backbone using acetal monomers, a structure as shown in Formula II is obtained. Formula II; Where A is an aromatic unit; B is a rigid twisted structural unit; Q is an electron-withdrawing group; a ≥ 10; b is any integer greater than or equal to 2; Aromatic unit A is one or more of the following groups: ； Rigid twisted structural unit B is one or more of the groups corresponding to the following compounds: ； Wherein, R1 is selected from one or more of hydrogen, C1-C10 alkyl, C1-C10 substituted alkyl, C6-C100 aromatic and C6-C100 substituted aromatic; the substituents in the substituted alkyl and substituted aromatic are each independently selected from halogens; The electron-withdrawing group Q is one or more of the following groups: ； Wherein, R2 is one or more of hydrogen, C1-C10 alkyl, C1-C10 substituted alkyl, C6-C100 aromatic or C6-C100 substituted aromatic; the substituents in the substituted alkyl and substituted aromatic are each independently selected from halogens.

2. The ionomer according to claim 1, characterized in that, For the structure shown in Equation II, when b=2, its structure is as shown in Equation (1); when b=3, its structure is as shown in Equation (2). When b=4, its structure is as shown in equation (3); as the value of b continues to increase, the corresponding structure is deduced accordingly. 。 3. A method for preparing the ionopolymer according to any one of claims 1 to 2, comprising the following steps: S1. Disperse acetal monomer D, aromatic monomer A' and rigid twisted monomer B' in dichloromethane, then mix with catalyst and stir until the viscosity of the reaction solution increases to the point that it cannot be stirred by a magnetic stirrer. After washing and drying, the polymer precursor is obtained. S2, Quaternization reaction: The polymer precursor is mixed with dimethyl sulfoxide solvent, the resulting mixed solution is mixed with a halogenated compound, and the reaction is stirred under light-protected conditions. After the reaction is completed, the mixture is washed and dried to obtain an ionic polymer. Alternatively, the polymer precursor can be mixed with dimethyl sulfoxide solvent, and the resulting mixed solution can be mixed with a halogenated compound and a base. The mixture can be stirred and reacted under light-protected conditions. After the reaction is complete, the mixture can be washed and dried to obtain an ionic polymer.

4. The preparation method according to claim 3, characterized in that, The aromatic monomer A' is one or more of the following compounds; 。 5. The preparation method according to claim 3, characterized in that, The rigid twisted monomer B' is one or more of the following compounds; ； Wherein, R1 is selected from one or more of hydrogen, C1-C10 alkyl, C1-C10 substituted alkyl, C6-C100 aromatic and C6-C100 substituted aromatic; the substituents in the substituted alkyl and substituted aromatic are each independently selected from halogens.

6. The preparation method according to claim 3, characterized in that, The acetal monomer D has the structure shown in Formula III; Formula III; Where Q is an electron-withdrawing group; R3 is selected from one or more of C1-C10 alkyl groups, C1-C10 substituted alkyl groups, C6-C100 aromatic groups, and C6-C100 substituted aromatic groups; the substituents in the substituted alkyl groups and substituted aromatic groups are each independently selected from halogens; The catalyst is at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, and perfluorosulfonic acid resin. The halogenated compound is at least one selected from monoiodoalkyl, monobromoalkyl, 2-bromoethylamine, 2-bromoethanol, ethyl 2-chloromethacrylate, 4-vinylbenzyl chloride, 1-(chloromethyl)-4-ethynylbenzene, 1-azido-4-(chloromethyl)benzene, 2-(chloromethyl), (5-bromopentyl)trimethylammonium bromide, and ethylene oxide.

7. A cross-linked ionic polymer, prepared by reacting an ionic polymer with a cross-linking agent; wherein the ionic polymer is the ionic polymer according to any one of claims 1 to 2, or the ionic polymer prepared by the preparation method according to any one of claims 3 to 6.

8. An ion exchange membrane, prepared from the ion polymer of any one of claims 1 to 2, or the ion polymer prepared by the preparation method of any one of claims 3 to 6, or the cross-linked ion polymer of claim 7.

9. The application of the ion exchange membrane according to claim 8 in flow batteries, hydrogen production by water electrolysis, fuel cells, electrochemical ammonia synthesis, carbon dioxide reduction, salinity gradient energy conversion, electrodialysis, lithium extraction from salt lakes, or wastewater treatment.

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