A side-chain quinine polymer, its preparation method, and its application in the preparation of anion exchange membranes.

Abstract

This invention provides a side-chain quinine polymer, its preparation method, and its application in the preparation of anion exchange membranes, belonging to the fields of fuel cells and water electrolysis for hydrogen production. First, an aromatic monomer, a functional monomer, and a quinine monomer are synthesized into a quinine polymer with good alkali resistance via a superacid-catalyzed condensation reaction. Second, a side-chain quinine polymer is prepared based on the synthesized quinine polymer. Finally, the side-chain quinine polymer is used as the main chain polymer for casting, and a high-performance all-carbon chain anion exchange membrane is obtained through side-chain grafting modification. The alkaline anion exchange membrane prepared by this invention exhibits excellent chemical stability, ionic conductivity, and mechanical properties, demonstrating superior overall performance. It can be applied in alkaline fuel cells, water electrolysis, energy storage batteries, carbon dioxide conversion, electrodialysis, and other electrochemical device fields.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of fuel cells and hydrogen production by water electrolysis, and relates to a side-chain quinuclidine-based polymer, a preparation method and application of the side-chain quinuclidine-based polymer in preparation of an anion exchange membrane. TECHNICAL BACKGROUND

[0002] At present, over-reliance on and exploitation of fossil energy result in a series of problems such as environmental pollution, energy shortage and greenhouse effect, and the global community urgently needs to develop green and clean renewable hydrogen energy to replace fossil fuels, among which, hydrogen production by water electrolysis and fuel cell technology have great development prospects as hydrogen energy conversion technology. As one of the key components of hydrogen production by water electrolysis and fuel cell technology, an anion exchange membrane can separate cathode and anode, transport ions, carry catalysts and prevent fuel leakage, and plays an important role in long-term stable operation of hydrogen production by water electrolysis and fuel cells. However, in order to meet the actual application of commercialization, the anion exchange membrane still has shortcomings such as poor stability and low conductivity, and researchers continue to conduct a large amount of scientific research to improve its conductivity and long-term stability in alkaline conditions.

[0003] Firstly, different polymer backbones are studied, including poly (arylene ether), poly (norbornene), poly (benzimidazole) and ether-free aromatic hydrocarbon polymer, etc. Among them, ether-containing polymers are easily eroded and degraded by the original nucleus of hydroxide, resulting in poor durability and dimensional stability; in contrast, all-carbon polymer backbones are gradually replacing ether-containing polymers due to their good alkali resistance, chemical stability and mechanical strength. Secondly, various ion transport groups are introduced into the polymer backbone or side chain, aiming to improve the ion transport performance and alkali resistance of the anion exchange membrane, among which, quinuclidine exhibits excellent alkali resistance in the form of a rigid bicyclic cation similar to a sphere, has a low ring strain and a constrained conformation, and is not prone to degradation reaction in high-concentration alkali solution, so quinuclidine-based polymers have excellent alkali resistance as a new type of anion exchange membrane material. However, as of now, the ion transport performance of quinuclidine-based anion exchange membranes has not been fully tapped, and it is still difficult to meet the requirements of commercial application. SUMMARY

[0004] In view of the above shortcomings of the prior art, the present application aims to provide a side-chain quinuclidine-based polymer and a preparation method of an anion exchange membrane thereof by designing the structure of the quinuclidine-based polymer molecular chain, so as to solve the problems of chemical stability, ion transport performance and mechanical stability of the existing quinuclidine-based anion exchange membrane.

[0005] To solve the above technical problems, the technical scheme of the present application is as follows:

[0006] A side-chain quinine polymer, comprising a quinine ring structural unit, an aromatic structural unit Ar1, a functional structural unit R1, and a side-chain structure R3, wherein the structure of the side-chain quinine polymer is shown in formula (P) or formula (Q):

[0007]

[0008] Where x is the molar percentage of the side chain structural unit in the polymer chain, %; y is the molar percentage of the functional structural unit in the polymer chain, %; z is the molar percentage of the quinine ring structural unit in the polymer chain, %; in formula P, x is 10%-50%, z is 50%-90%; in formula Q, x is 10%-50%, y is 0%-40%, z is 25%-90%.

[0009] Preferably, the R1 structure is at least one of the following:

[0010]

[0011] In the R1 structure, R2 is hydrogen or a C1-C10 alkyl group.

[0012] Preferably, the Ar1 structure is at least one of the following aryl monomer structures:

[0013]

[0014] In the Ar1 structure, R2 is either hydrogen or C1-C. 10 Alkyl groups.

[0015] Preferably, R3 includes at least one of the following structures:

[0016]

[0017] In the R3 structure, R2 is hydrogen or a C1-C10 alkyl group.

[0018] A method for preparing a side-chain quinine polymer includes the following steps:

[0019] The first step is to synthesize quinine polymers;

[0020] Ar1 was dissolved in dichloromethane. After dissolution, 3-quinone or a mixture of 3-quinone and R1 was added. Trifluoromethanesulfonic acid was added dropwise. The reaction was stirred at a certain temperature. When the reaction liquid became very viscous and climbed the rod, the reaction was stopped. The reaction liquid was poured into deionized water for precipitation, washing, filtration, and drying to obtain the quinoline polymer.

[0021] The reaction temperature is 20–30°C, and the reaction time is 4–24 hours.

[0022] The monomer has a molar concentration of 1.0–2.0 mol / L in dichloromethane;

[0023] When Ar1 is added to 3-quinone, the molar ratio of Ar1 to 3-quinone is 1:(1-1.5); when Ar1 is added to a mixture of 3-quinone and R1, the molar ratio of Ar1, 3-quinone, and R1 is 1:(1-1.5):(0.01-0.5).

[0024] The molar ratio of 3-quinone to trifluoromethanesulfonic acid is 1:4 to 9;

[0025] The drying temperature is 80℃ and the drying time is 24 hours.

[0026] The second step is to prepare a side-chain quinine polymer;

[0027] The quinine polymer prepared in the first step was dissolved in solvent X. Then, potassium carbonate, brominated R3, and iodomethane were added to the mixture, and the mixture was reacted at a certain temperature in the dark for a period of time. After the reaction, the mixed solution was precipitated in precipitant A, purified, and dried to obtain the target solid.

[0028] The reaction temperature is 20–80°C, and the reaction time is 12–48 h.

[0029] The molar ratio of the quinine polymer: brominated R3: iodomethane: potassium carbonate is 1:(0.1-0.5):1.5:2;

[0030] The quinine polymer has a mass concentration of 0.01–0.05 g / mL in solvent X;

[0031] The solvent X is one or a mixture of two or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone;

[0032] The precipitant A is one or a mixture of two or more of the following: diethyl ether, methanol, ethanol, ethyl acetate, acetone, and water.

[0033] The drying temperature is 80℃ and the reaction time is 24h.

[0034] An application of a side-chain quinine polymer for preparing a side-chain quinine polymer anion exchange membrane, wherein the OH... - Type I anion exchange membranes have the structures shown in formulas (S) and (T):

[0035]

[0036] The preparation method includes the following steps:

[0037] Further, the dried side-chain quinine polymer was dissolved in solvent Y to prepare a membrane solution, which was then filtered, degassed, and poured onto a clean plate for drying to obtain an anion exchange membrane. This anion exchange membrane was then immersed in KOH solution at room temperature until sufficient ion exchange was achieved. Afterward, it was washed with deionized water until neutral and dried to obtain an OH- ion exchange membrane. - The resulting polymer anion exchange membrane exhibits good ion transport performance, alkali resistance, and dimensional stability, thus providing a side-chain quinine-based polymer anion exchange membrane.

[0038] The concentration of the membrane solution is 3-10 wt%.

[0039] The drying temperature is 60-80℃, and the time is 6-24 hours.

[0040] The soaking time is 24–48 hours, and the concentration of the KOH solution is 1–2 mol / L.

[0041] The solvent Y is one or a mixture of two or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0042] The present invention has the following beneficial effects:

[0043] (1) The innovation of this invention is as follows: synthesizing an ether-free polymer backbone and a strong alkali-resistant cationic group to improve the intrinsic alkali resistance of AEMs; based on the essence of microphase separation morphology construction, combined with a long-range grafting strategy, using cation-dipole driving force to induce the directional aggregation of hydrophilic ion domains to construct high-speed ion transport water channels, improving ion conductivity while maintaining dimensional stability; and using large-volume aromatic hydrophobic structural units to introduce more free volume in the membrane, breaking the tight packing and interlocking between linear molecular chains, facilitating the movement of the backbone and cationic groups, while increasing the molecular weight of the polymer and improving steric hindrance, reducing the OH-induced alkali resistance. - Risk of attack.

[0044] (2) This invention enables the preparation of side-chain quinine polymer anion exchange membranes through the design of quinine polymer molecules. These membranes possess excellent mechanical strength and ion transport performance, with an ionic conductivity greater than 150 mS / cm at 80°C. -1 It exhibits excellent alkali resistance, at 2 mol L... -1 After soaking in KOH solution for 10,000 hours, its ionic conductivity does not decrease, which can meet the application requirements of hydrogen production by water electrolysis, fuel cells and energy storage batteries. Attached Figure Description

[0045] Figure 1 The 1H NMR spectrum of the anion exchange membrane in Experiment Example 1;

[0046] Figure 2 The water absorption and swelling rate curves of the anion exchange membrane in Experiment Example 1 are shown.

[0047] Figure 3 The mechanical properties of the anion exchange membrane in Experiment Example 2;

[0048] Figure 4 The ionic conductivity is the anion exchange membrane in Experiment Example 4. Detailed Implementation

[0049] The present invention will be further described below with reference to specific implementation examples.

[0050] Test methods involved in the embodiments:

[0051] Ion conductivity testing: The ionic conductivity of AEMs was measured using a CHI660E electrochemical workstation. A 1cm × 4cm sample was prepared and immersed in deionized water for 24 hours before testing. The thickness (T, cm) and width (W, cm) of the wet film were recorded. The sample was then laid flat on the test electrode, and a four-electrode AC impedance mode was used. The temperature range was set from 30℃ to 80℃. Each sample was tested three times at each temperature, and the average value was taken. The formula for calculating σ is as follows:

[0052]

[0053] Where L represents the distance between the electrode plates (cm); R represents the impedance of the AEMs (Ω).

[0054] Water absorption and swelling rate: 1cm × 4cm AEMs samples were immersed in deionized water at 30℃~80℃ for 24h, and the surface moisture was quickly wiped dry. Their mass (W) was then measured. wet ) and length (L) wet The sample was then dried to constant weight, and its dry weight (W) was measured. dry ) and length (L) dry The formulas for calculating WU and SR are as follows:

[0055]

[0056]

[0057] Mechanical property testing: The mechanical properties of AEMs were tested using a material testing machine (Instron-5567A). The membrane was cut into strips of 0.6cm × 3cm, with an effective test size of 0.6cm × 2cm. The tests were conducted at room temperature and a tensile rate of 1mm / min. Each sample was tested 5 times and the average value was taken.

[0058] Example 1:

[0059] Step 1: Preparation of side-chain quinine polymers (in this example, x is 10%, y is 0%, and z is 90%):

[0060] In this implementation, Ar1 was selected as terphenyl. R3 is propane.

[0061] 3-quinine cyclohexanone and p-terphenyl were added to a three-necked flask equipped with a mechanical stirrer, with a molar ratio of 3-quinine cyclohexanone to p-terphenyl of 1.5:1. In this example, 1.88 g of 3-quinine cyclohexanone and 2.30 g of p-terphenyl were added. Dichloromethane was added and stirred to dissolve the monomers to a total concentration of 2 mol / L. Trifluoromethanesulfonic acid was slowly added dropwise under ice bath conditions, with a molar ratio of 3-quinine cyclohexanone to trifluoromethanesulfonic acid of 1:9. In this example, 13.5 g of trifluoromethanesulfonic acid was added. The mixture was heated to 20°C and reacted for 24 h. The reaction was stopped when the reaction liquid became very viscous and began to climb the rod. The reaction solution was washed in deionized water until neutral and dried at 80°C for 24 h to obtain the quinine polymer. 2 g of quinyl polymer was dissolved in dimethyl sulfoxide to make a solution concentration of 0.01 g / mL. Brominated R3 (1-bromopropane in this example), iodomethane, and potassium carbonate were added to the solution, with a molar ratio of quinyl polymer to 1-bromopropane, iodomethane, and potassium carbonate of 1:0.1:1.5:2. In this example, the quinyl polymer was 2 g, 1-bromopropane was 0.074 g, iodomethane was 0.64 g, and potassium carbonate was 0.83 g. The mixture was reacted at 80 °C in the dark for 12 h. After the reaction, the mixture was precipitated in diethyl ether, purified, and dried at 80 °C for 24 h to obtain the target solid, i.e., the side-chain quinyl polymer.

[0062] Part Two: Applications of Side-Chain Quinol Polymers in the Preparation of Anion Exchange Membranes

[0063] A 10 wt% solution of the above-mentioned 1 g side-chain quinine polymer was prepared by dissolving it in dimethyl sulfoxide. The solution was filtered, degassed, and poured onto a clean glass plate. It was then dried at 60 °C for 24 h to obtain an anion exchange membrane. This membrane was immersed in 2 M KOH solution for 24 h. After sufficient ion exchange, it was washed with deionized water until neutral and dried to obtain an OH- ion exchange membrane. - Type polymer anion exchange membrane.

[0064] analyze: Figure 1 In this embodiment, the side-chain quinine polymer was subjected to 1H NMR spectroscopy. 1 Characterization results (H-NMR). Figure 1Several strong peaks are observed in the 7.30–7.80 ppm range, corresponding to the characteristic peaks of hydrogen atoms on the aromatic ring. A broad peak at 4.30 ppm, a small peak at 3.52 ppm, two broad peaks at 3.21 ppm and 3.13 ppm, and two broad peaks at 1.95 ppm and 1.79 ppm correspond to protons at the aH, bH, cH, and dH sites of the quinine ring, respectively. The presence of alkyl proton signals in the 0.8–1.7 ppm range indicates successful side grafting.

[0065] Example 2:

[0066] Step 1: Preparation of side-chain quinine polymers (in this example, x is 50%, y is 25%, and z is 25%):

[0067] In this implementation, Ar1 was selected as meta-terphenyl. R1 is 2,3-butanedione R3 is 1-pentyl fluorine. 3-quinone, p-terphenyl, and 2,3-butanedione were added to a three-necked flask equipped with a mechanical stirrer in a molar ratio of 0.75:1:0.25. In this example, 0.95 g of 3-quinone, 2.30 g of p-terphenyl, and 0.22 g of 2,3-butanedione were added. Dichloromethane was added and stirred to dissolve the monomers to a total concentration of 1 mol / L. Trifluoromethanesulfonic acid was slowly added dropwise under ice bath conditions, with a molar ratio of 3-quinone to trifluoromethanesulfonic acid of 1:4. In this example, 6.0 g of trifluoromethanesulfonic acid was added. The mixture was heated to 30°C and reacted for 4 hours. The reaction was stopped when the reaction liquid became very viscous and began to climb the rod. The reaction solution was washed in deionized water until neutral and dried at 80°C for 24 hours to obtain the quinyl polymer. 2 g of quinyl polymer was dissolved in N-methylpyrrolidone to make a solution concentration of 0.05 g / mL. Brominated R3 (5-bromopentylfluoro in this example), iodomethane, and potassium carbonate were added to the solution, with the molar ratio of quinyl polymer to 1-bromo-5-fluoropentane, iodomethane, and potassium carbonate being 1:0.5:1.5:2. In this example, the quinyl polymer was 2 g, 1-bromo-5-fluoropentane was 0.51 g, iodomethane was 0.64 g, and potassium carbonate was 0.83 g. The mixture was reacted at 20 °C in the dark for 48 h. After the reaction, the mixture was precipitated in ethyl acetate, purified, and dried at 80 °C for 24 h to obtain the target solid, i.e., the side-chain quinyl polymer.

[0068] Part Two: Applications of Side-Chain Quinol Polymers in the Preparation of Anion Exchange Membranes

[0069] A 3wt% solution was prepared by dissolving 1g of the above-mentioned side-chain quinine polymer in N-methylpyrrolidone. The solution was filtered, degassed, and poured onto a clean glass plate. It was then dried at 80°C for 6 hours to obtain an anion exchange membrane. This membrane was immersed in 1M KOH solution for 48 hours. After sufficient ion exchange, it was washed with deionized water until neutral and dried to obtain an OH- ion exchange membrane. - Type polymer anion exchange membrane.

[0070] analyze: Figure 2 This is a characterization of the water absorption and swelling rate of the side-chain quinine-based anion exchange membrane in this embodiment. Figure 2 The variation of water absorption and swelling rate of fully hydrated side-chain quinine-based anion exchange membranes within the temperature range of 30-80℃ is shown in the figure. As can be seen from the figure, the water absorption and swelling rate of all membranes exhibits a positive correlation with temperature, which is consistent with objective laws. The water absorption and swelling rate of the membrane is largely influenced by the backbone and side chains. At 30℃, the water absorption and swelling rates are 60.00% and 10.14%, respectively, demonstrating good dimensional stability.

[0071] Example 3:

[0072] Step 1: Preparation of side-chain quinine polymers (in this example, x is 30%, y is 17%, and z is 50%):

[0073] In this embodiment, Ar1 was selected as 9,9-dimethylfluorene. R1 is 2,3,4-trifluoroacetophenone R3 is 1-butyl-4-fluorobenzene 3-quinone, trifluoroacetophenone, and 9,9-dimethylfluorene were added to a three-necked flask equipped with a mechanical stirrer in a molar ratio of 1.25:0.25:1. In this example, 1.56 g of 3-quinone, 0.49 g of 9,9-dimethylfluorene, and 1.74 g of 2,3,4-trifluoroacetophenone were added. Dichloromethane was added and stirred to dissolve the monomers to a total concentration of 1.5 mol / L. Trifluoromethanesulfonic acid was slowly added dropwise under ice bath conditions, with a molar ratio of 3-quinone to trifluoromethanesulfonic acid of 1:6.5. In this example, 6.0 g of trifluoromethanesulfonic acid was added. The mixture was heated to 25°C and reacted for 14 h. The reaction was stopped when the reaction liquid became very viscous and began to climb the rod. The reaction solution was washed in deionized water until neutral and dried at 80°C for 24 h to obtain the quinyl polymer. 2 g of quinyl polymer was dissolved in N,N-dimethylformamide to make a solution concentration of 0.03 g / mL. Brominated R3 (1-(4-bromobutyl)-4-fluorobenzene in this example), iodomethane, and potassium carbonate were added to the solution, with a molar ratio of quinyl polymer to 1-(4-bromobutyl)-4-fluorobenzene, iodomethane, and potassium carbonate of 1:0.3:1.5:2. In this example, the quinyl polymer was 2 g, 1-(4-bromobutyl)-4-fluorobenzene was 0.42 g, iodomethane was 0.64 g, and potassium carbonate was 0.83 g. The mixture was reacted at 50 °C in the dark for 30 h. After the reaction, the mixture was precipitated in ethanol, purified, and dried at 80 °C for 24 h to obtain the target solid, i.e., the side-chain quinyl polymer.

[0074] Part Two: Applications of Side-Chain Quinol Polymers in the Preparation of Anion Exchange Membranes

[0075] 1 g of the above-mentioned side-chain quinine polymer was dissolved in N,N-dimethylacetamide to prepare a 6 wt% solution. The solution was filtered, degassed, and poured onto a clean glass plate. It was then dried at 70°C for 15 h to obtain an anion exchange membrane. This membrane was immersed in 1.5 M KOH solution for 36 h. After sufficient ion exchange, it was washed with deionized water until neutral and dried to obtain an OH- ion exchange membrane. - Type polymer anion exchange membrane.

[0076] Analysis: The mechanical properties of the prepared side-chain quinine-based anion exchange membrane were tested, and the results are as follows: Figure 3 As shown, the tensile strength of the membrane is 30.03 MPa, and the elongation at break is 15.82%. It can be observed that with the introduction of side chains, the elongation at break increases, while the tensile strength decreases. The prepared AEMs exhibit excellent mechanical properties, meeting the application requirements of fuel cells.

[0077] Example 4:

[0078] Step 1: Preparation of side-chain quinine polymers (in this example, x is 20%, y is 40%, and z is 40%):

[0079] In this implementation, Ar1 was selected as biphenyl. R1 is pentafluorobenzaldehyde R3 is 1-methylpiperidinoctane 3-quinone, pentafluorobenzaldehyde, and biphenyl were added to a three-necked flask equipped with a mechanical stirrer in a molar ratio of 0.6:0.4:1. In this example, 0.75 g of 3-quinone, 0.78 g of pentafluorobenzaldehyde, and 1.54 g of biphenyl were added. Dichloromethane was added and stirred to dissolve the monomers, bringing the total concentration to 1.2 mol / L. Trifluoromethanesulfonic acid was slowly added dropwise under ice bath conditions, with a molar ratio of 3-quinone to trifluoromethanesulfonic acid of 1:6. In this example, 9.0 g of trifluoromethanesulfonic acid was added. The mixture was heated to 25°C and reacted for 14 h. The reaction was stopped when the reaction liquid became very viscous and began to climb the rod. The reaction solution was washed in deionized water until neutral and dried at 80°C for 24 h to obtain the quinyl polymer. 2 g of quinyl polymer was dissolved in N,N-dimethylacetamide to make a solution concentration of 0.02 g / mL. Brominated R3 (1-(8-bromooctyl)methylpiperidine in this example), iodomethane, and potassium carbonate were added to the solution. The molar ratio of quinyl polymer to 1-(8-bromooctyl)methylpiperidine, iodomethane, and potassium carbonate was 1:0.2:1.5:2. In this example, the amount of quinyl polymer was 2 g, 1-(8-bromooctyl)methylpiperidine was 0.35 g, iodomethane was 0.64 g, and potassium carbonate was 0.83 g. The mixture was reacted at 65 °C in the dark for 20 h. After the reaction, the mixture was precipitated in ethyl acetate, purified, and dried at 80 °C for 24 h to obtain the target solid, i.e., the side-chain quinyl polymer.

[0080] Part Two: Applications of Side-Chain Quinol Polymers in the Preparation of Anion Exchange Membranes

[0081] 1 g of the above-mentioned side-chain quinine polymer was dissolved in N,N-dimethylacetamide to prepare a 4 wt% solution. The solution was filtered, degassed, and poured onto a clean glass plate. It was then dried at 65°C for 20 h to obtain an anion exchange membrane. This membrane was immersed in 1.56 M KOH solution for 30 h. After sufficient ion exchange, it was washed with deionized water until neutral and dried to obtain an OH- ion exchange membrane. - Type polymer anion exchange membrane.

[0082] analyze: Figure 4 This describes the ionic conductivity characterization of the side-chain quinine-based anion exchange membrane in this embodiment. As temperature increases, the ion migration rate of the membrane accelerates, and the OH... - The conductivity exhibits a positive correlation with temperature. Its conductivity at 30℃ is 68.0 mS / cm. -1At 80℃, it is 163.2 mS cm. -1 It has excellent ionic conductivity.

[0083] Example 5:

[0084] Step 1: Preparation of side-chain quinine polymers (in this example, x is 30%, y is 10%, and z is 60%):

[0085] In this implementation, Ar1 was selected as diphenylethane. R1 is 1-butaneindigo R3 is 1-quininehexane. 3-quinone, N-butaneindigo, and diphenylethane were added to a three-necked flask equipped with a mechanical stirrer in a molar ratio of 0.9:0.1:1. In this example, 1.13 g of 3-quinone, 0.20 g of N-butaneindigo, and 1.82 g of diphenylethane were added. Dichloromethane was added and stirred to dissolve the monomers, bringing the total concentration to 1.3 mol / L. Trifluoromethanesulfonic acid was slowly added dropwise under ice bath conditions, with a molar ratio of 3-quinone to trifluoromethanesulfonic acid of 1:7. In this example, 10.51 g of trifluoromethanesulfonic acid was added. The mixture was heated to 26°C and reacted for 10 h. The reaction was stopped when the reaction liquid became very viscous and began to climb the rod. The reaction solution was washed in deionized water until neutral and dried at 80°C for 24 h to obtain the quinyl polymer. 2 g of quinyl polymer was dissolved in dimethyl sulfoxide to make a solution concentration of 0.03 g / mL. Brominated R3 (6(bromoalkyl)-1-quinine in this example), iodomethane, and potassium carbonate were added to the solution. The molar ratio of quinyl polymer to 6(bromoalkyl)-1-quinine, iodomethane, and potassium carbonate was 1:0.3:1.5:2. In this example, the amount of quinyl polymer was 2 g, 6(bromoalkyl)-1-quinine was 0.49 g, iodomethane was 0.64 g, and potassium carbonate was 0.83 g. The mixture was reacted at 60 °C in the dark for 20 h. After the reaction, the mixture was precipitated in methanol, purified, and dried at 80 °C for 24 h to obtain the target solid, i.e., the side-chain quinyl polymer.

[0086] Part Two: Applications of Side-Chain Quinol Polymers in the Preparation of Anion Exchange Membranes

[0087] 1 g of the above-mentioned side-chain quinine polymer was dissolved in N,N-dimethylacetamide to prepare a 4 wt% solution. The solution was filtered, degassed, and poured onto a clean glass plate. It was then dried at 65°C for 20 h to obtain an anion exchange membrane. This membrane was immersed in 1.7 M KOH solution for 27 h. After sufficient ion exchange, it was washed with deionized water until neutral and dried to obtain an OH- ion exchange membrane. - Type polymer anion exchange membrane.

[0088] Example 6:

[0089] Step 1: Preparation of side-chain quinine polymers (in this example, x is 25%, y is 17%, and z is 58%):

[0090] In this implementation, Ar1 was selected as o-terphenyl. and para-tetraphenyl R1 is 2-thienylcarbaldehyde R3 is 1-butyl-1-methylpiperidinbutane. 3-quinone, 2-thiophenecarboxaldehyde, o-terphenyl, and p-tetraphenyl were added to a three-necked flask equipped with a mechanical stirrer in a molar ratio of 1.25:0.25:0.5:0.5. In this example, 1.56 g of 3-quinone, 0.28 g of 2-thiophenecarboxaldehyde, 1.15 g of o-terphenyl, and 1.53 g of p-tetraphenyl were added. Dichloromethane was added and stirred to dissolve the monomers to a total concentration of 1.1 mol / L. Trifluoromethanesulfonic acid was slowly added dropwise under ice bath conditions, with a molar ratio of 3-quinone to trifluoromethanesulfonic acid of 1:5. In this example, 7.50 g of trifluoromethanesulfonic acid was added. The mixture was heated to 15°C and reacted for 21 h. The reaction was stopped when the reaction liquid became very viscous and began to climb the rod. The reaction solution was washed in deionized water until neutral and dried at 80°C for 24 h to obtain the quinyl polymer. 2 g of quinyl polymer was dissolved in dimethyl sulfoxide to make a solution concentration of 0.025 g / mL. Brominated R3 (1-bromo-5-methylpiperidine nonane in this example), iodomethane, and potassium carbonate were added to the solution. The molar ratio of quinyl polymer to 1-bromo-5-methylpiperidine nonane, iodomethane, and potassium carbonate was 1:0.25:1.5:2. In this example, the amount of quinyl polymer was 2 g, 1-bromo-5-methylpiperidine nonane was 0.42 g, iodomethane was 0.64 g, and potassium carbonate was 0.83 g. The mixture was reacted at 75 °C in the dark for 13 h. After the reaction was complete, the mixture was precipitated in methanol, purified, and dried at 80 °C for 24 h to obtain the target solid, i.e., the side-chain quinyl polymer.

[0091] Part Two: Applications of Side-Chain Quinol Polymers in the Preparation of Anion Exchange Membranes

[0092] A 5.5 wt% solution of the above-mentioned 1 g side-chain quinine polymer was prepared by dissolving it in N,N-dimethylformamide. The solution was filtered, degassed, and poured onto a clean glass plate. It was then dried at 65°C for 20 h to obtain an anion exchange membrane. This membrane was immersed in 1.8 M KOH solution for 27 h to allow for sufficient ion exchange. Afterward, it was washed with deionized water until neutral and dried to obtain an OH- ion exchange membrane. - Type polymer anion exchange membrane.

[0093] Example 7:

[0094] Step 1: Preparation of side-chain quinine polymers (in this example, x is 20%, y is 15%, and z is 65%):

[0095] In this implementation, the Ar1 selected is N-ethylcarbazole. R1 is 1,3-difluoroacetophenone R3 is valeronitrile and 8-(butyl)-8-methyl-5,8-diazaspiro[4,5]decane 3-quinone, 1,3-difluoroacetophenone, and N-ethylcarbazole were added to a three-necked flask equipped with a mechanical stirrer in a molar ratio of 1.1:0.2:1. In this example, 1.38 g of 3-quinone, 0.31 g of 1,3-difluoroacetophenone, and 1.95 g of N-ethylcarbazole were added. Dichloromethane was added and stirred to dissolve the monomers to a total concentration of 1.3 mol / L. Trifluoromethanesulfonic acid was slowly added dropwise under ice bath conditions, with a molar ratio of 3-quinone to trifluoromethanesulfonic acid of 1:5.5. In this example, 8.25 g of trifluoromethanesulfonic acid was added. The mixture was heated to 16°C and reacted for 23 h. The reaction was stopped when the reaction liquid became very viscous and began to climb the rod. The reaction solution was washed in deionized water until neutral and dried at 80°C for 24 h to obtain the quinyl polymer. 2g of quinyl polymer was dissolved in N,N-dimethylacetamide to make the solution concentration 0.04g / mL. Brominated R3 (in this example, 1-bromopentanilide and 8-(4-bromobutyl)-8-methyl-5,8-diazaspiro[4.5]decane), iodomethane, and potassium carbonate were added to the solution. The molar ratio of quinyl polymer to 1-bromopentanilide, 8-(4-bromobutyl)-8-methyl-5,8-diazaspiro[4.5]decane, iodomethane, and potassium carbonate was 1:0.1:0.1:1.5:2. In this example, the quinyl polymer was 2g, 1-bromopentanilide was 0.097g, 8-(4-bromobutyl)-8-methyl-5,8-diazaspiro[4.5]decane was 0.14g, iodomethane was 0.83g, and potassium carbonate was 0.83g. The mixture was reacted at 50°C in the dark for 30h. After the reaction was completed, the mixed solution was precipitated in ethanol, purified, and dried at 80°C for 24 hours to obtain the target solid, which is the side-chain quinine polymer.

[0096] Part Two: Applications of Side-Chain Quinol Polymers in the Preparation of Anion Exchange Membranes

[0097] A 6.5 wt% solution of the above-mentioned 1 g side-chain quinine polymer was prepared by dissolving it in dimethyl sulfoxide. The solution was filtered, degassed, and poured onto a clean glass plate. It was then dried at 60 °C for 20 h to obtain an anion exchange membrane. This membrane was immersed in a 1.5 M KOH solution for 36 h to allow for sufficient ion exchange. Afterward, it was washed with deionized water until neutral and dried to obtain an OH- ion exchange membrane. - Type polymer anion exchange membrane.

[0098] Example 8:

[0099] Step 1: Preparation of side-chain quinine polymers (in this example, x is 30%, y is 21%, and z is 49%):

[0100] In this implementation, Ar1 was selected as meta-terphenyl. and para-terphenyl R1 is 1,3-dibromoacetone R3 is N-hexyl-N-(5-fluoropentyl)-4-methylpiperidine and heptane 3-quinone, 1,3-dibromoacetone, m-terphenyl, and p-terphenyl were added to a three-necked flask equipped with a mechanical stirrer in a molar ratio of 1.1:0.3:0.6:0.4. In this example, 1.38 g of 3-quinone, 0.64 g of 1,3-dibromoacetone, 1.38 g of m-terphenyl, and 0.92 g of p-terphenyl were added. Dichloromethane was added and stirred to dissolve the monomers to a total concentration of 1.3 mol / L. Trifluoromethanesulfonic acid was slowly added dropwise under ice bath conditions, with a molar ratio of 3-quinone to trifluoromethanesulfonic acid of 1:3. In this example, 4.50 g of trifluoromethanesulfonic acid was added. The mixture was heated to 24°C and reacted for 20 h. The reaction was stopped when the reaction liquid became very viscous and began to climb the rod. The reaction solution was washed in deionized water until neutral and dried at 80°C for 24 h to obtain the quinyl polymer. 2 g of quinyl polymer was dissolved in N,N-dimethylformamide to make a solution concentration of 0.07 g / mL. Brominated R3 (in this example, N-(6-bromohexyl)-N-(5-fluoropentyl)-4-methylpiperidine bromide and 1-bromoheptane), iodomethane, and potassium carbonate were added to the solution. The molar ratio of quinyl polymer to N-(6-bromohexyl)-N-(5-fluoropentyl)-4-methylpiperidine bromide, 1-bromoheptane, iodomethane, and potassium carbonate was 1:0.2:0.1:1.5:2. In this example, the amount of quinyl polymer was 2 g, N-(6-bromohexyl)-N-(5-fluoropentyl)-4-methylpiperidine bromide was 0.42 g, 1-bromoheptane was 0.11 g, iodomethane was 0.14 g, and potassium carbonate was 0.83 g. The mixture was reacted at 50°C in the dark for 30 h. After the reaction was completed, the mixed solution was precipitated in ethanol, purified, and dried at 80°C for 24 hours to obtain the target solid, which is the side-chain quinine polymer.

[0101] Part Two: Applications of Side-Chain Quinol Polymers in the Preparation of Anion Exchange Membranes

[0102] A 4.5 wt% solution of the above-mentioned 1 g side-chain quinine polymer was prepared by dissolving it in dimethyl sulfoxide. The solution was filtered, degassed, and poured onto a clean glass plate. It was then dried at 50 °C for 24 h to obtain an anion exchange membrane. This membrane was immersed in a 1.5 M KOH solution for 36 h to allow for sufficient ion exchange. Afterward, it was washed with deionized water until neutral and dried to obtain an OH- ion exchange membrane. - Type polymer anion exchange membrane.

[0103] The above embodiments are merely illustrative of the implementation methods of the present invention, but should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the protection scope of the present invention.

Claims

1. A side-chain quinine polymer, characterized in that, The side-chain quinine polymer comprises a quinine ring structural unit, an aromatic structural unit Ar1, a functional structural unit R1, and a side-chain structure R3. The structure of the side-chain quinine polymer is as follows: Q Where x represents the molar percentage of the side-chain structural unit in the polymer chain (%), y represents the molar percentage of the functional structural unit in the polymer chain (%), and z represents the molar percentage of the quinine ring structural unit in the polymer chain (%). In formula Q, x is 10%-50%, y is 0%-40%, and z is 25%-90%; The R1 structure is at least one of the following: Wherein, R2 in the R1 structure is hydrogen or a C1-C10 alkyl group; The aromatic structural unit Ar1 is formed from at least one of the following aromatic structural monomers: In the Ar1 structure, R2 is either hydrogen or C1-C. 10 Alkyl groups; The cationic group in R3 includes at least one of the following structures, wherein the anion is OH. - : In the R3 structure, R2 is a C1-C10 alkyl group.

2. A method for preparing the side-chain quinine polymer according to claim 1, characterized in that, Includes the following steps: The first step is to synthesize quinine polymers; The aromatic monomer is dissolved in an organic solvent. After dissolution, 3-quinone or a mixture of 3-quinone and the functional monomer corresponding to R1 is added. Trifluoromethanesulfonic acid is added dropwise. The reaction is stirred at a certain temperature. The reaction is stopped when the reaction liquid becomes very viscous and climbs the rod. The reaction liquid is poured into deionized water for precipitation, washing, filtration, and drying to obtain the quinoline polymer. The second step is to prepare a side-chain quinine polymer; The quinoline polymer obtained in the first step was dissolved in solvent X. Then, potassium carbonate, bromoR3, and iodomethane were added to the mixture and reacted at a certain temperature in the dark for a period of time. After the reaction, the mixed solution was precipitated in precipitant A, purified and dried to obtain the side-chain quinoline polymer.

3. The method for preparing a side-chain quinine polymer according to claim 2, characterized in that, In the first step: The reaction temperature is 20~30℃, and the reaction time is 4~24h; The molar concentration of the aromatic monomer in the organic solvent is 1.0~2.0 mol / L; When 3-quinone is added to the aromatic monomer, the molar ratio of the aromatic monomer to 3-quinone is 1:(1-1.5), and the molar ratio of 3-quinone to trifluoromethanesulfonic acid is 1:4~9. When the aromatic monomer is added to a mixture of 3-quinone and functional monomer, the molar ratio of the aromatic monomer, 3-quinone, and functional monomer is 1:(1-1.5):(0.01-0.5), and the molar ratio of 3-quinone to trifluoromethanesulfonic acid is 1:4~9.

4. The method for preparing a side-chain quinine polymer according to claim 2, characterized in that, In the second step: The reaction temperature is 20~80℃, and the reaction time is 12~48h; The molar ratio of the quinine polymer: brominated R3: iodomethane: potassium carbonate is 1:(0.1-0.5):1.5:2; The quinine polymer has a mass concentration of 0.01~0.05 g / mL in solvent X.

5. The method for preparing a side-chain quinine polymer according to claim 2, characterized in that: The drying temperature in the first step is 80℃ and the drying time is 24h; the drying temperature in the second step is 80℃ and the reaction time is 24h. The organic solvent in the first step is dichloromethane; the solvent X in the second step is one or a mixture of two or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. In the second step, precipitant A is one or a mixture of two or more of the following: diethyl ether, methanol, ethanol, ethyl acetate, acetone, and water.

6. An application of the side-chain quinine polymer according to claim 1, characterized in that, The side-chain quinine polymer is used to prepare a side-chain quinine polymer anion exchange membrane, having the structure shown in the following formula: 。 7. The application of a side-chain quinine polymer according to claim 6, characterized in that, The method for preparing a side-chain quinine polymer anion exchange membrane is as follows: the dried side-chain quinine polymer is dissolved in solvent Y to form a membrane solution, which is then subjected to filtration, degassing, casting, alkaline immersion, water washing until neutral, and drying to obtain the side-chain quinine polymer anion exchange membrane.

8. The application of a side-chain quinine polymer according to claim 7, characterized in that: The concentration of the membrane solution is 3-10 wt%; The drying temperature is 60-80℃, and the time is 6-24 hours. The soaking time is 24-48 hours, and the alkaline solution is a 1-2 mol / L KOH solution; The solvent Y is one or a mixture of two or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

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