Branched agglomerated aryl cyclamine anion exchange membrane containing multiple cationic groups as well as preparation method and application of branched agglomerated aryl cyclamine anion exchange membrane

Abstract

The invention discloses a branched polyaryl cyclic amine anion exchange membrane containing various cationic groups, a preparation method and application thereof. In an acidic catalytic system, an aromatic compound, a highly branched aromatic compound, a carbonyl substance and polycyclic aromatic hydrocarbon are subjected to a condensation polymerization reaction in a dichloromethane medium to form the polyaryl cyclic amine polymeric membrane material with polycation and highly branched structures. The polymer is subjected to quaternization modification treatment to obtain an anion exchange functional group, then the anion exchange functional group is transformed into an OH <-> form in an alkaline solution, and finally a thin film material with multiple types of ion transmission sites is prepared through a thermal evaporation process. According to the process, a synergistic effect mechanism of a multi-cationic group and a highly branched aromatic skeleton is creatively adopted, and a series of anion exchange membrane products suitable for different industrial scene requirements can be prepared by adjusting polymer composition and membrane forming parameters, and the anion exchange membrane has the remarkable characteristics of excellent ionic conduction performance and structural designability.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of anion exchange membrane materials, and particularly relates to a branched polyaromatic cyclic amine anion exchange membrane containing multiple types of cationic groups, a preparation method thereof, and ion transmission applications. BACKGROUND

[0002] Electrolysis of water to produce hydrogen is one of the important ways to obtain high-purity hydrogen, especially the electrolysis of water using renewable energy electricity, i.e., "green hydrogen" production, which is currently a hot research and industrialization topic. The technology of electrolysis of water using anion exchange membranes combines the advantages of alkaline electrolysis of water and proton exchange membrane electrolysis of water, and has the characteristics of high electrolysis efficiency, fast response speed, and low cost, and is considered as one of the most promising hydrogen production technologies in the future. This technology uses an anion exchange membrane as an electrolyte to produce hydrogen and oxygen by electrolysis of water, which provides the possibility for large-scale application of hydrogen energy.

[0003] As a core component in the system of electrolysis of water to produce hydrogen, the performance of an anion exchange membrane (AEM) directly determines the efficiency and service life of the entire system. The main function of AEM is to achieve efficient conduction of hydroxyl ions (OH⁻) while blocking gas crossover to prevent hydrogen and oxygen from mixing. However, existing AEM technologies still face many challenges. On the one hand, the ionic conductivity of AEM is generally low, which limits the efficiency of electrolysis of water; on the other hand, in a high-temperature and strong alkaline environment, the chemical stability and mechanical properties of AEM are insufficient, resulting in poor durability. In addition, the preparation process and material cost of AEM are also important factors affecting its large-scale application. Therefore, developing an anion exchange membrane with high ionic conductivity, excellent chemical stability, and mechanical properties is of great significance for promoting the development of electrolysis of water to produce hydrogen technology.

[0004] Currently, most anion exchange membranes are based on polyaromatic piperidines and polyaromatic quinines, which introduce quaternary ammonium cation groups to achieve the transmission of anions. However, piperidinium cations are prone to degradation in alkaline environments, such as Hofmann elimination, which leads to insufficient chemical stability and durability of the membrane, thereby affecting the service life of fuel cells and other equipment. In addition, although some polyaromatic quinine materials have certain stability, there is still much room for improvement in their structural design and performance optimization, and their high cost also makes it difficult to meet the growing demand for high performance. Chinese Patent 202410126815.8 discloses a preparation method of a nitrogen-containing multi-component copolymer anion exchange membrane, but its structure is linear, and no branched structure design is performed. The linear polymer backbone often lacks entanglement of polymer chains, resulting in low conductivity, mechanical strength, and alkali resistance.

[0005] In summary, it is of great practical significance to develop a polyaryl cyclic amine anion exchange membrane with multiple types of cationic groups and a highly branched polymer skeleton. This not only overcomes the shortcomings of existing technologies, but also provides more efficient and stable material support for the development of new energy technologies, promoting technological progress and industrial upgrading in related fields. SUMMARY

[0006] In view of the current limited multi-cation group anion exchange membrane materials, insufficient chemical stability and durability, and insufficient conductivity, mechanical strength and alkali resistance of linear polymer skeleton, the purpose of the present application is to develop a new type of polyaryl cyclic amine anion exchange membrane with multiple types of cationic groups and a highly branched polymer skeleton.

[0007] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows: One of the purposes of the present application is: Based on the strong designability of polyaryl piperidine and polyaryl quinine, a series of branched polyaryl cyclic amine anion exchange membranes with multiple types of cationic groups can be designed and constructed by designing the unit to realize functionalization, and a series of branched polyaryl cyclic amine anion exchange membranes with multiple types of cationic groups having the following structural units shown in formula (1), formula (2) or formula (3) are designed: Formula (1), Formula (2), Formula (3); Wherein, A is selected from any one of the following structures: ; B is selected from any one of the following structures: ; R1 is selected from at least two different structures: ; Wherein, a is any integer greater than or equal to 1; b is any integer greater than or equal to 0.

[0008] Preferably, the branched polyaryl cyclic amine anion exchange membrane with multiple types of cationic groups proposed by the present application has the following structural formula: Or .

[0009] The second purpose of the present application is: The present application also provides a preparation method of the branched polyaryl cyclic amine anion exchange membrane with multiple types of cationic groups, comprising the following steps: The aromatic compound and the carbonyl compound are added to an organic solvent, and then the reaction is carried out under the condition of strong acid catalysis in an ice bath, after the reaction is completed, neutralization, washing and drying are carried out, and a polyaryl material is obtained; The halogenated polyaryl material is stirred with a halogenated hydrocarbon reagent, and then the halogenated polyaryl material is dissolved in a solvent to form a solution, the solution is cast on a glass plate, and the solution is evaporated to obtain a halogenated polyaryl anion exchange membrane material. The halogenated polyaryl anion exchange membrane material is soaked in an X- anion solution for ion exchange, and an X- type branched polyaryl cyclic amine anion exchange membrane containing multiple types of cationic groups is obtained.

[0010] Preferably, the aromatic compound includes a linear aromatic hydrocarbon compound A and a branched aromatic hydrocarbon compound B.

[0011] Preferably, the linear aromatic hydrocarbon compound A is biphenyl, p-terphenyl, 1,3,5-triphenylbenzene or 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene.

[0012] Preferably, the carbonyl compound is N-methyl-4-piperidone, 3-quinuclidone or 2,2,2-trifluorophenylacetone.

[0013] Preferably, the reaction temperature of the ice bath reaction is 0-5℃, and the reaction time is 72-96 hours.

[0014] Preferably, in the step of dissolving the halogenated polyaryl material in a solvent to form a solution, the solvent is selected from at least one of N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide and sulfolane.

[0015] Preferably, the halogenated hydrocarbon is iodomethane.

[0016] Preferably, in the step of stirring the polyaryl material with the halogenated hydrocarbon reagent, the stirring temperature is 40-50℃, and the stirring time is 24-48 hours.

[0017] Preferably, the mass ratio of the polyaryl material to the halogenated hydrocarbon is 2:1.

[0018] Preferably, in the step of soaking the halogenated polyaryl anion exchange membrane material in an X- anion solution for ion exchange, the ion exchange temperature is 75-85℃, and the exchange time is 24-48 hours.

[0019] The third object of the present application is to provide a branched polyaryl cyclic amine anion exchange membrane containing multiple types of cationic groups. The present application also provides the use of the branched polyaryl cyclic amine anion exchange membrane containing multiple types of cationic groups in an alkaline anion exchange membrane fuel cell.

[0020] Compared with the prior art, the application has the following beneficial effects: The branched polyaromatic amine anion exchange membrane containing multiple cationic groups is provided in the application, multiple cationic groups and highly branched aromatic compounds are introduced into the polyaromatic anion exchange membrane at the same time for the first time, multiple cationic groups are used as ion transmission exchange sites, the degradation reaction of the exchange membrane material in an alkaline environment is weakened, the chemical stability and durability of the anion exchange membrane are improved, and the service life of the anion membrane fuel cell is correspondingly improved. Meanwhile, the branched network structure is formed in the anion exchange membrane by introducing the branched directional core B, the entanglement of the polymer chain is increased, the mechanical strength and alkali resistance stability of the anion exchange membrane are improved, and the conductivity of the anion exchange membrane is further improved, so that the anion exchange membrane material has application potential.

[0021] (2) The preparation method of the polyaromatic amine material containing multiple cationic groups provided by the application first uses multiple carbonyl compound monomers, such as 1-methyl-4-piperidone and 3-quinuclidone, to react with aromatic compounds (such as biphenyl, p-terphenyl, 1,3,5-triphenylbenzene, and the like) in an organic solvent under acidic conditions to prepare multiple polyaromatic amine materials containing multiple cationic groups, and then the final product is obtained through quaternization, film preparation, and ion exchange. The product has excellent ion transmission performance. The synthesis process of the application is simple, the cost is low, and the application has broad industrial application prospects. BRIEF DESCRIPTION OF DRAWINGS

[0022] The accompanying drawings, which form a part of this application, are included to provide a further understanding of the application and are incorporated in and constitute a part of this application. The embodiments illustrated in the drawings, and their description, are presented to explain the application and are not intended to limit the application. In the drawings: Figure 1 The nuclear magnetic resonance hydrogen spectrum (1H-NMR) of the anion exchange membrane in Example 1.

[0023] Figure 2 The nuclear magnetic resonance hydrogen spectrum (1H-NMR) of the anion exchange membrane in Example 2.

[0024] Figure 3 The synthesis route diagram of the polyaromatic amine material containing multiple cationic groups T1a in Example 1.

[0025] Figure 4 The synthesis route diagram of the polyaromatic amine material containing multiple cationic groups B1a in Example 2. DETAILED DESCRIPTION

[0026] The various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the application.

[0027] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. Additionally, for a range of values of, for example, a parameter, an individual value from the range can be expressly disclosed herein to mean that each and every intermediate value of the range is also expressly disclosed. All individual values and subranges from the recited range are specifically included in the present application. The upper and lower limits of these intervening ranges can be independently combined with any other intervening range or sub-range to produce other disclosed ranges and sub-ranges. These disclosures are meant to be included within the scope of the present application.

[0028] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned herein are incorporated by reference to disclose and describe the methods and / or materials in connection with which the documents are cited. In case of conflict between the present specification and any document incorporated by reference, the present specification will control.

[0029] Various modifications and changes can be made to the specific embodiments described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those of ordinary skill in the art from the description and examples herein. The description and examples are illustrative only.

[0030] As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having", "contains", "containing", or variations thereof, are intended to be open-ended terms that mean including, but not limited to.

[0031] A branched polycation-containing group-containing polyaryl cyclic amine anion exchange membrane is disclosed, having the following chemical formula: , ,

[0032] wherein a is any integer greater than or equal to 1; b is any integer greater than or equal to 0; A represents a linear aromatic hydrocarbon compound, including at least one of the following phenyl structural monomers: ; B represents a branched aromatic hydrocarbon compound, including at least one of the following phenyl structural monomers: ; R1 is a carbonyl compound, including at least two of the following carbonyl structural monomers: ; When A, B and R1 are selected from a plurality of types, the combinations are random, and the arrangement of different combinations is also random.

[0033] In one aspect of the present application, the ion transport performance and chemical stability of the membrane are improved by introducing different cationic groups, such as a plurality of cationic groups. In another aspect, the water absorption, dimensional stability and mechanical properties of the membrane are effectively improved by introducing a branched structure, such as designing a new polymer backbone, increasing the length and degree of branching of the side chain, and the like, thereby further improving the comprehensive performance of the membrane.

[0034] In a second aspect of the present application, a preparation method of the above-mentioned anion exchange membrane material is provided, comprising: Step 1: linear aromatic compound A, branched aromatic compound B and at least two different carbonyl compounds are added to an organic solvent, and an ice bath reaction is carried out at 0-5°C under the catalysis of a strong acid for 72-96 hours. After the reaction is completed, neutralization, washing and drying are carried out to obtain a phosphorus-containing polyaryl material; Step 2: the polyarylammonium material containing a plurality of types of cationic groups is stirred with a halogenated hydrocarbon reagent such as iodomethane at room temperature for 48-72 hours to obtain a polyarylammonium material containing a plurality of types of cationic groups of formula I - , which is then dissolved in DMSO and cast on a glass plate. The solution is evaporated to obtain a branched polyarylammonium material containing a plurality of types of cationic groups of formula I - . The mass ratio of iodomethane to the polyarylammonium material containing a plurality of types of cationic groups is 2:1; Step 3: the branched polyarylammonium material containing a plurality of types of cationic groups of formula I - is immersed in an X-alkaline anion solution at 75-80°C for ion exchange for 24-48 hours to obtain a polyarylammonium material containing a plurality of types of cationic groups of formula X.

[0035] In some preferred embodiments of the present application, the aromatic compound is biphenyl, p-terphenyl, 1,3,5-triphenylbenzene, 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene, etc.

[0036] In some preferred embodiments of the present application, the carbonyl compound is N-methyl-4-piperidone, 3-quinuclidone and 2,2,2-trifluorophenylacetone, etc.

[0037] In some preferred embodiments of the present application, the X-alkaline anion solution is a KOH solution with a concentration of 1M.

[0038] The method of the present application is further illustrated below with reference to examples. In the following examples, the instruments and apparatuses used are conventional in the art, and the various raw materials and reagents used are commercially available unless otherwise specified, and are used in conventional specifications, or can be prepared or formulated by known methods or according to the instructions of the reagents. The experimental methods in the following examples, unless otherwise specified, are generally carried out under conventional conditions, or according to the conditions recommended by the manufacturer.

[0039] Example 1 Into a 25 mL round bottom flask, 1,3,5-triphenylbenzene (76.6 mg, 0.25 mmol), p-terphenyl (1094.5 mg, 4.75 mmol) were added as solvents, 1-methyl-4-piperidone (0.29 mL, 2.5 mmol) and 3-quinuclidone (312.9 mg, 2.5 mmol) were added, then the flask was immersed in an ice bath and stirred for ten minutes, trifluoromethanesulfonic acid (2-5 mL) was added. Then stirred at low temperature for 48-72 hours, the reaction stopped when the viscous liquid in the flask could not be stirred. After the reaction stopped, the liquid was poured into a mixture of methanol (100 mL) and 1M KOH (100 mL), the solid was completely precipitated. Washed with 1M KOH and water several times until neutral, vacuum dried at 100°C for 12h to obtain the product, cationic group-containing polymer T1a, with a yield of 93.5%. The structural formula of T1a is:

[0040] Into a glass bottle, 500 mg of T1a and 400 mg of potassium carbonate were weighed, 15 mL of DMSO and 0.5 mL of iodomethane were added, and the reaction was carried out at room temperature in the dark for 48 h. After 48 h, white solid was obtained by pouring into ethyl acetate, washed once with ethyl acetate, twice with water, and vacuum dried at 100°C to obtain the product, quaternary ammonium salt type polymer T1b, with a yield of 89.2%.

[0041] 500 mg of T1b was dispersed in 20 mL of DMSO, and ultrasonic was used to completely dissolve it. The solution was cast on a glass petri dish with a smooth surface, dried at 80°C for 6h, and at 120°C for 12h to obtain a smooth I - anion exchange membrane T1c.

[0042] The membrane T1c was soaked in 1M KOH, and ion exchange was carried out at 80°C for 48h to obtain the OH-type anion exchange membrane T1d.

[0043] The synthesis process of Example 1 and the product are shown in Figure 3 The proton nuclear magnetic resonance spectrum (1H-NMR) of the anion exchange membrane prepared is shown in Figure 1 .

[0044] T1d has a tensile strength of 65.1 MPa. At 80 °C, T1d has an electrical conductivity of 210.7 mS / cm, a swelling ratio of 12.5%, a water uptake of 15.9%, and no degradation after 1500 h of immersion in 1 M KOH. T1d was used as a separator for anion exchange membrane water electrolysis (AEMWE) and the AEM cell reached a peak current density of 2.65 A / cm2(80 °C, 2.0 V). 2 (80 °C, 2.0 V).

[0045] Example 2 2,2'-Bis(diphenylphosphino)-1,1 '-binaphthyl (155.7 mg, 0.25 mmol), p-terphenyl (1094.5 mg, 4.75 mmol) were added into a 25 mL round bottom flask, dichloromethane (10 mL) was added as solvent, followed by 1 -methyl-4-piperidinone (0.29 mL, 2.5 mmol) and 3-quinuclidinone (312.9 mg, 2.5 mmol), then the flask was immersed in an ice bath and stirred for ten minutes, trifluoromethanesulfonic acid (2-5 mL) was added. Then the reaction was stirred at low temperature for 48-72 hours, the reaction stopped when the viscous liquid in the flask could not be stirred. After the reaction stopped, the liquid was poured into a mixture of methanol (100 mL) and 1 M KOH (100 mL), the solid was completely precipitated. Then washed with 1 M KOH and water several times until neutral, dried at 100 °C under vacuum for 12 h to obtain the product, cationic group-containing polymer B1a, with a yield of 92.6%. The structural formula of B1a is:

[0046] 500 mg of B1a and 400 mg of potassium carbonate were weighed into a glass bottle, 15 mL of DMSO and 0.5 mL of iodomethane were added, and the reaction was carried out at room temperature in the dark for 48 h. After 48 h, white solid was obtained by pouring into ethyl acetate, washed once with ethyl acetate, twice with water, and dried at 100 °C under vacuum to obtain the product, quaternary ammonium salt type polymer B1b, with a yield of 91.9%.

[0047] 500 mg of B1b was dispersed in 20 mL of DMSO, and ultrasonic was used to completely dissolve it. The solution was cast on a glass petri dish with a smooth surface, dried at 80 °C for 6 h, and at 120 °C for 12 h to obtain a smooth I - anion exchange membrane B1c.

[0048] The membrane B1c was immersed in 1 M KOH and ion exchanged at 80 °C for 48 h to obtain the OH-type anion exchange membrane B1d.

[0049] The synthesis process of Example 2 and the product are shown in Figure 4, the 1H-NMR of the prepared anion exchange membrane is as follows Figure 2 .

[0050] The tensile strength of B1d can reach 80.8 MPa. The conductivity of B1d can reach 207.2 mS / cm at 80℃, the swelling rate is 13.7%, the water absorption rate is 18.1%, and there is no degradation phenomenon after soaking in 1M KOH for 1500h. B1d is used as a separator for anion exchange membrane electrolysis of water to produce hydrogen, and the AEM electrolytic cell reaches a peak current density of 2.54 A / cm 2 (80℃, 2.0V).

[0051] The above is only a preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto, any person skilled in the art can easily think of changes or replacements within the technical scope disclosed by the present application, which should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A branched polycationic group-containing polyarylcyclic amine anion exchange membrane, characterized by, The branched polyarylcyclic amine anion exchange membrane containing multiple types of cationic groups has a structural unit shown in formula (1), formula (2) or formula (3), Formula (1), Formula (2), Formula (3); Wherein, A is selected from any one of the following structures: ； B is selected from any one of the following structures: ； R1 is selected from at least two different ones of the following structures: ； Wherein, a is any integer greater than or equal to 1; b is any integer greater than or equal to 0.

2. A process for the preparation of branched polycationic group containing polyarylcyclic amine based anion exchange membranes as claimed in claim 1, characterized in that, The method comprises the following steps: adding the aromatic compound and the carbonyl compound into an organic solvent, and performing ice bath reaction under the condition of strong acid catalysis, and after the reaction is completed, neutralization, washing and drying are performed to obtain a polyaryl material; stirring the polyaryl material and a halogenated hydrocarbon reagent to obtain a halogenated polyaryl material, dissolving the halogenated polyaryl material in a solvent to form a solution, pouring the solution on a glass plate, and evaporating the solution to obtain a halogenated polyaryl anion exchange membrane material; immersing the halogenated polyaryl anion exchange membrane material in an X- anion solution to perform ion exchange, and obtaining an X- type branched polyarylcyclic amine anion exchange membrane containing multiple types of cationic groups.

3. The method of making branched polycationic group-containing poly(arylene) cyclic amine-based anion exchange membranes according to claim 2, characterized in that, The aromatic compound includes a linear aromatic compound A and a branched aromatic compound B.

4. The method of making branched polycationic group-containing poly(arylene) cyclic amine anion exchange membranes according to claim 2, wherein, The molar ratio of the aromatic compound to the carbonyl compound is 1:

1.

5. The method of making branched polycationic group-containing poly(arylene) cyclic amine anion exchange membranes according to claim 2, wherein, The reaction temperature of the ice bath reaction is 0-5 DEG C, and the reaction time is 72-96 hours.

6. The method of making branched polycationic group-containing poly(arylene) cyclic amine anion exchange membranes according to claim 2, characterized in that, In the step of dissolving the halogenated polyaryl material in a solvent to form a solution, at least one of N-methylpyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide and sulfolane is selected as the solvent.

7. The method of making branched polycationic group-containing poly(arylene) cyclic amine-based anion exchange membranes according to claim 2, wherein, The halogenated hydrocarbon is methyl iodide.

8. The method of making branched polycationic group-containing poly(arylene) cyclic amine anion exchange membranes according to claim 2, wherein, In the step of stirring the polyaryl material and the halogenated hydrocarbon reagent, the stirring temperature is 40-50 DEG C, the stirring time is 24-48 hours, and the mass ratio of the polyaryl material to the halogenated hydrocarbon is 2:

1.

9. The method of making branched polycationic group-containing poly(arylene) cyclic amine anion exchange membranes according to claim 2, wherein, In the step of immersing the halogenated polyaryl anion exchange membrane material in an X- anion solution to perform ion exchange, the ion exchange temperature is 75-85 DEG C, and the exchange time is 24-48 hours.

10. The branched polyarylcyclic amine anion exchange membrane containing multiple types of cationic groups in claim 1 is applied in an alkaline anion exchange membrane fuel cell.

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