A grafted flexible side chain cationic group containing sulfide ether flexible spacer anion exchange membrane material and a preparation method and application thereof

Abstract

The application provides a grafted flexible side chain cation group sulfur ether flexible spacer anion exchange membrane material, a molecular structure formula of the anion exchange membrane material is shown as formula 1: the formula 1 is divided into a flexible side chain functionalized structure unit and a non-functionalized structure unit, the content of the flexible side chain functionalized structure unit is x=0.25-0.40; the content of the non-functionalized structure unit is 1-x=0.60-0.75; n=350-1000, the toughness of the polymer membrane material is improved by introducing a sulfur ether flexible spacer on a polymer main chain; the ion conductivity is improved by synergistically introducing a piperidine ion salt with a long flexible side chain to form a double piperidine structure, and the alkali resistance stability of the polymer membrane material can also be improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of ion exchange membrane and its preparation, and particularly relates to a grafted flexible side chain cationic group containing sulfide flexible spacer anion exchange membrane material and its preparation method and application. BACKGROUND

[0002] With the continuous optimization of energy structure, the development and large-scale utilization of environmentally friendly renewable energy is imperative, which is of great significance to solve energy shortage and improve the environment. The development of new green energy conversion devices such as water electrolysis hydrogen production is an effective method to realize the utilization of environmentally friendly renewable energy. In the technology of water electrolysis hydrogen production, anion exchange membrane water electrolysis fully combines the advantages of alkaline water electrolysis and proton membrane water electrolysis, and has the characteristics of low cost, high efficiency and sustainable production of green hydrogen under alkaline conditions, and has developed rapidly. As the core component, the stability and conductivity of the anion exchange membrane directly affect the purity of H2 and O2, the power consumption and the service life of the water electrolysis cell.

[0003] Anion exchange membrane is mainly composed of polymer backbone, cationic group and freely movable anion. At present, polyphenyl ether, polyaryl ether sulfone, polyaryl ether ketone and other polymers have been widely used as the main chain of anion exchange membrane. However, the oxygen atoms contained in the polymer main chain are easily attacked by hydroxyl ions under alkaline conditions, and the anion exchange membrane will be damaged and the ion conductivity will decrease, which hinders the transformation of anion exchange membrane water electrolysis cell from laboratory scale to commercial application. Then scholars have developed an oxygen-free main chain anion exchange membrane of polyaryl piperidine, which has a chemical structure mainly composed of aromatic rings and excellent chemical stability.

[0004] However, since the piperidine ion in the oxygen-free main chain is directly connected to the polymer main chain, the random distribution of the rigid backbone and the cation makes it difficult for the membrane material to form an effective microphase separation structure, and thus it is difficult to achieve satisfactory ion conductivity. At the same time, the rigid aromatic backbone makes the prepared anion exchange membrane have poor toughness, and sometimes cannot meet the requirements of water electrolysis tank in assembly and operation. Therefore, the poor toughness, the balance between ion conductivity and dimensional stability are still the problems to be solved for the existing oxygen-free main chain anion exchange membrane. SUMMARY

[0005] The purpose of the present application is to solve the above problems, and provide a grafted flexible side chain cationic group containing sulfide flexible spacer anion exchange membrane material and its preparation method and application, which aims to improve the toughness of the polymer membrane material by introducing a sulfide flexible spacer on the polymer main chain; by synergistically introducing piperidine ion salt with long flexible side chain, forming a double piperidine structure to improve the ion conductivity, and also improving the alkali resistance of the polymer membrane material.

[0006] In one aspect, the application provides a grafting flexible side chain cationic group containing sulfide flexible spacer anion exchange membrane material, the molecular structure of the anion exchange membrane material is shown as formula 1:

[0007]

[0008] The formula 1 is divided into flexible side chain functionalized structure unit and non-functionalized structure unit, the content of the flexible side chain functionalized structure unit x = 0.25-0.40; the content of the non-functionalized structure unit 1-x = 0.60-0.75; n = 350-1000.

[0009] In a second aspect, the application provides a preparation method of grafting flexible side chain cationic group containing sulfide flexible spacer anion exchange membrane material, the reaction route equation is:

[0010]

[0011] The specific steps are as follows:

[0012] Step A. Preparation of sulfide flexible spacer polyphenylene sulfide piperidine polymer: phenyl sulfide, 1-methyl-4-piperidone and dichloromethane are added to a three-necked flask, stirred under ice bath conditions, trifluoromethanesulfonic acid is added, and the reaction is continued under ice bath conditions, then the ice bath is removed, and the reaction is continued at room temperature. After dilution with dichloromethane, a white fine strip-shaped solid is obtained by settling in alkaline solution. The solid is separated and washed with deionized water several times until it is neutral, and then dried to obtain a sulfide flexible spacer polyphenylene sulfide piperidine polymer;

[0013] The structure of the sulfide flexible spacer polyphenylene sulfide piperidine polymer is shown as formula 2:

[0014]

[0015] Step B. Preparation of 6-bromohexyl-1-methylpiperidine bromide: 1,6-dibromohexane and ethyl acetate are added to a three-necked flask equipped with a stirrer, N2 inlet, and stirred under heating conditions. Then, a mixture of 1-methylpiperidine and ethyl acetate is added dropwise to the three-necked flask through a constant pressure funnel, and the mixture is further stirred. After the reaction is completed, the product is filtered and washed with ethyl acetate several times, and then dried to obtain a white solid powder of 6-bromohexyl-1-methylpiperidine bromide;

[0016] The reaction equation of this step is:

[0017]

[0018] The structure of 6-bromohexyl-1-methylpiperidine bromide is shown as formula 3:

[0019]

[0020] Step C. Preparation of the grafted flexible side chain cationic group containing sulfide flexible spacer anion exchange membrane material: the sulfide flexible spacer polyphenylene sulfide piperidine polymer prepared in step A and N-methyl pyrrolidone are added to a three-necked flask with nitrogen inlet and outlet, heated and stirred, K2CO3 is added first after the polymer is completely dissolved, then the 6-bromohexyl-1-methyl piperidine bromide prepared in step B is added, after the reaction is completed, the reaction liquid is filtered with a G4 sand core funnel and poured into a prepared membrane container, dried to obtain the grafted flexible side chain cationic group containing sulfide flexible spacer anion exchange membrane.

[0021] Further, in step A, the molar ratio of diphenyl sulfide and 1-methyl-4-piperidone is 1:1-1:1.3.

[0022] Further, in step A, the molar ratio of triflic acid and 1-methyl-4-piperidone is 3:1-4:1.

[0023] Further, in step B, the amount of 1,6-dibromohexane is 3-5 times that of 1-methyl piperidine, the reaction temperature is 40-60 DEG C, and the reaction time is 6-12 h.

[0024] Further, in step C, the amount of N-methyl pyrrolidone is 30-60 times the mass of the sulfide flexible spacer polyphenylene sulfide piperidine polymer.

[0025] Further, in step C, the molar ratio of the amount of K2CO3 to the sulfide flexible spacer polyphenylene sulfide piperidine polymer is 1:1.

[0026] Further, in step C, the molar ratio of the amount of 6-bromohexyl-1-methyl piperidine bromide to the sulfide flexible spacer polyphenylene sulfide piperidine polymer is 0.25:1-0.4:1.

[0027] The third aspect of the application also provides the application of the grafted flexible side chain cationic group containing sulfide flexible spacer anion exchange membrane material, which can be applied to an alkaline water electrolysis cell as a key component.

[0028] Compared with the prior art, the application has the following beneficial effects:

[0029] (1) The application designs and synthesizes a grafted flexible side chain cationic group sulfur ether flexible spacer anion exchange membrane material, which introduces a sulfur ether flexible spacer on the polymer main chain to improve the toughness of the polymer membrane material; by introducing a piperidine ion salt with a long flexible side chain, the alkali resistance stability of the polymer membrane material is further improved; and a double piperidine structure is formed to further improve the ion conductivity of the polymer membrane material.

[0030] (2) The grafted flexible side chain cationic group sulfur ether flexible spacer polymer provided by the application can be dissolved in N-methyl pyrrolidone, and an ion exchange membrane is prepared by a casting film method, and the prepared ion exchange membrane has good ion conductivity, dimensional stability and chemical stability, and can be used as an ion exchange membrane material in an alkaline water electrolyzer for hydrogen production. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 The synthesis route of the grafted flexible side chain cationic group sulfur ether flexible spacer anion exchange membrane material is shown in the application;

[0032] Figure 2 The nuclear magnetic resonance spectrum of the 6-bromohexyl-1-methyl piperidine bromide prepared in Example 1 of the application is shown in the application;

[0033] Figure 3 The nuclear magnetic resonance spectrum of the sulfur ether flexible spacer-containing polymer prepared in Example 1 of the application is shown in the application;

[0034] Figure 4 The nuclear magnetic resonance spectrum of the grafted flexible side chain cationic group sulfur ether flexible spacer polymer prepared in Example 3 of the application is shown in the application;

[0035] Figure 5 The ion conductivity graph of the grafted flexible side chain cationic group sulfur ether flexible spacer polymer anion exchange membrane described in Examples 1, 2, 3 and 4 of the application is shown in the application;

[0036] Figure 6 The alkali resistance stability graph of the grafted flexible side chain cationic group sulfur ether flexible spacer polymer anion exchange membrane described in Example 3 of the application is shown in the application;

[0037] Figure 7 The water electrolyzer performance graph of the grafted flexible side chain cationic group sulfur ether flexible spacer polymer anion exchange membrane described in Example 3 of the application is shown in the application. DETAILED DESCRIPTION

[0038] In order to make the above-mentioned purposes, features and advantages of the application more obvious and easy to understand, the specific embodiments of the application will be described in detail below with reference to the description examples. The methods are all conventional methods unless otherwise specified, and the raw materials can be obtained from public commercial channels unless otherwise specified.

[0039] As used in this description, the terms "one embodiment" or "an embodiment” mean a specific implementation of features, structures or characteristics that can be included in at least one implementation of the present disclosure. The appearances of the terms "in one embodiment” or "in an embodiment” in various places in this specification do not necessarily refer to the same embodiment, nor do they necessarily refer to any one embodiment. Rather, they mean one or more implementations of the present disclosure.

[0040] The sources of the drugs and reagents used in the embodiments are as follows:

[0041] 1,6-dibromohexane: Acros Organics, >98.0%

[0042] 1-methylpiperidine: Acros Organics, >97.0%

[0043] Ethyl acetate: Shanghai Lingfeng Chemical Reagent Co., Ltd., AR

[0044] Phenyl sulfide: Acros Organics, >98%

[0045] 1-methyl-4-piperidone: Acros Organics, >98%

[0046] Trifluoromethanesulfonic acid: Acros Organics, 99%

[0047] Dichloromethane: Shanghai Lingfeng Chemical Reagent Co., Ltd., AR

[0048] N-methylpyrrolidone: aladdin, >99.5%

[0049] Potassium carbonate: Shanghai Lingfeng Chemical Reagent Co., Ltd., >99.0%.

[0050] The synthesis was carried out according to the reaction equation route map shown in Figure 1

[0051] The specific preparation method is as follows:

[0052] Step A. Preparation of a sulfide-containing flexible spacer polyphenylene sulfide piperidine polymer: phenyl sulfide, 1-methyl-4-piperidone and dichloromethane were added to a three-necked flask, stirred under ice bath conditions, trifluoromethanesulfonic acid was added thereto, and the reaction was continued under ice bath conditions. After removing the ice bath, the reaction was continued at room temperature. After dilution with dichloromethane, the white fine strip-shaped solid was obtained by settling in a lye solution. The solid was separated and washed with deionized water several times until it was neutral. After drying, the sulfide-containing flexible spacer polyphenylene sulfide piperidine polymer was obtained;

[0053] ​Step B. Preparation of 6-bromohexyl-1-methylpiperidine bromide containing: In a three-necked flask equipped with a stirrer, N2 inlet and outlet, 1,6- dibromohexane and ethyl acetate were added to complete dissolution, after warming and stirring, a mixture of 1-methylpiperidine and ethyl acetate was added dropwise to the three-necked flask through a constant pressure funnel, and the mixture was further stirred, after the reaction was completed, the product was filtered and washed with ethyl acetate several times, then dried to obtain white solid powder containing 6-bromohexyl-1-methylpiperidine bromide;

[0054] Step C. Preparation of a flexible side chain cationic group containing sulfide flexible spacer anion exchange membrane material: the sulfide flexible spacer polyphenylene sulfide piperidine polymer prepared in step A and N-methyl pyrrolidone were added to a three-necked flask with nitrogen inlet and outlet, warmed and stirred, and after the polymer was completely dissolved, K2CO3 was first added, then 6-bromohexyl-1-methylpiperidine bromide prepared in step B was added, after the reaction was completed, the reaction liquid was filtered with a G4 sand core funnel and poured into a prepared membrane container, and after drying, a flexible side chain cationic group containing sulfide flexible spacer anion exchange membrane was obtained.

[0055] The following is a detailed description of the raw material feeding amount and specific reaction conditions in the examples.

[0056] Example 1

[0057] Step A. Preparation of a sulfide flexible spacer polyphenylene sulfide piperidine polymer: 3.7254 g (20 mmol) of phenylene sulfide, 2.38 g (21 mmol) of 1-methyl-4-piperidone and 10 mL of dichloromethane were added to a 100 mL three-necked flask, after stirring for 20 min under ice bath conditions, 6 mL (67 mmol) of triflic acid was slowly added, and after continuing to react for 30 min under ice bath conditions, the ice bath was removed, and the reaction was continued at room temperature for 12 h. After the system became highly viscous, it was diluted with dichloromethane and precipitated in a basic solution to obtain a white fine strip-shaped solid, which was separated and washed with deionized water several times until neutral, and then dried at 60°C for 24 h to obtain a polyphenylene sulfide piperidine polymer (PPSP);

[0058] The PPSP NMR spectrum measured by sampling is shown in Figure 2

[0059] ​Step B. Preparation of 6-bromohexyl-1-methylpiperidinium bromide: In a 100 mL three-necked flask equipped with a stirrer, N2inlet and outlet, 49.79 g of 1,6-dibromohexane (200 mmol) and 30 mL of ethyl acetate were added and stirred well at 60 °C for 30 min. Then, 4.09 g (40 mmol) of 1-methylpiperidine and 70 mL of ethyl acetate were added dropwise into the mixture through a constant pressure funnel and the mixture was further stirred for 12 h. After the reaction was completed, the product was filtered and washed with ethyl acetate several times. Then it was dried under vacuum at 60 °C for 12 h to obtain white solid powder of 6-bromohexyl-1-methylpiperidinium bromide (Br-6-Pip);

[0060] The Br-6-Pip NMR spectrum was measured by sampling as Figure 3

[0061] Step C. Preparation of grafted flexible side chain cationic group containing sulfide flexible spacer anion exchange membrane material: 0.60 g (2.1320 mmol) of PPSP and 15 mL of N-methylpyrrolidone were added to a 100 mL three-necked flask with nitrogen inlet and outlet, and stirred at 80 °C for about 30 min. After the polymer was completely dissolved, 0.06 g of K2CO3 (0.4264 mmol) was added first, then 0.1463 g of Br-6-Pip (0.4264 mmol) was added, and the reaction was completed after 3 days.

[0062] After the reaction solution was filtered with a G4 sand core funnel, it was poured into a prepared membrane holder, and after drying, the grafted flexible side chain cationic group containing sulfide flexible spacer anion exchange membrane PPSP-25Pip was obtained.

[0063] Example 2

[0064] Step A. Preparation of sulfide flexible spacer-containing polyphenylene sulfide piperidine polymer

[0065] The same as Step A of Example 1.

[0066] Step B. Preparation of 6-bromohexyl-1-methylpiperidinium bromide

[0067] The same as Step B of Example 1.

[0068] ​Step C. Preparation of the grafted flexible side chain cationic group sulfur-ether containing flexible spacer anion exchange membrane material: 0.60 g (2.1320 mmol) of PPSP and 15 mL of N-methyl pyrrolidone were added into a 100 mL three-necked flask with nitrogen inlet and outlet, and stirred at 80 °C for about 30 minutes. After the polymer was completely dissolved, 0.09 g of K2CO3 (0.6396 mmol) was first added, followed by the addition of 0.2195 g of Br-6-Pip (0.6396 mmol), and the reaction was completed after 3 days. The reaction solution was filtered with a G4 sand core funnel and poured into a prepared membrane holder, and after drying, the grafted flexible side chain cationic group sulfur-ether containing flexible spacer anion exchange membrane PPSP-30Pip was obtained.

[0069] Example 3

[0070] Step A. Preparation of the sulfur-ether containing flexible spacer polyphenylene sulfide piperidine polymer

[0071] The same as Example 1 Step A.

[0072] Step B. Preparation of the 6-bromohexyl-1-methylpiperidine bromide containing

[0073] The same as Example 1 Step B.

[0074] Step C. Preparation of the grafted flexible side chain cationic group sulfur-ether containing flexible spacer anion exchange membrane material: 0.60 g (2.1320 mmol) of PPSP and 15 mL of N-methyl pyrrolidone were added into a 100 mL three-necked flask with nitrogen inlet and outlet, and stirred at 80 °C for about 30 minutes. After the polymer was completely dissolved, 0.09 g of K2CO3 (0.6396 mmol) was first added, followed by the addition of 0.2195 g of Br-6-Pip (0.6396 mmol), and the reaction was completed after 3 days. The reaction solution was filtered with a G4 sand core funnel and poured into a prepared membrane holder, and after drying, the grafted flexible side chain cationic group sulfur-ether containing flexible spacer anion exchange membrane PPSP-30Pip was obtained.

[0075] The grafted flexible side chain cationic group sulfur-ether containing flexible spacer polymer NMR spectrum was measured by sampling as shown in Figure 4 .

[0076] The reaction solution was filtered with a G4 sand core funnel and poured into a prepared membrane holder, and after drying, the grafted flexible side chain cationic group sulfur-ether containing flexible spacer anion exchange membrane PPSP-35Pip was obtained.

[0077] Example 4

[0078] Step A. Preparation of the sulfur-ether containing flexible spacer polyphenylene sulfide piperidine polymer

[0079] The same as Example 1 Step A.

[0080] Step B. Preparation of the 6-bromohexyl-1-methylpiperidine bromide containing

[0081] The same as step B of Example 1.

[0082] Step C. Preparation of the grafted flexible side chain cationic group containing sulfide flexible spacer anion exchange membrane material: 0.60 g (2.1320 mmol) of PPSP and 15 mL of N-methylpyrrolidone were added to a 100 mL three-necked flask with nitrogen inlet and outlet, and stirred at 80°C for about 30 minutes. After the polymer was completely dissolved, 0.10 g of K2CO3 (0.7462 mmol) was first added, followed by 0.2561 g of Br-6-Pip (0.7462 mmol), and the reaction was completed after 3 days. The reaction liquid was filtered with a G4 sand core funnel and poured into a prepared membrane holder, and after drying, the grafted flexible side chain cationic group containing sulfide flexible spacer anion exchange membrane PPSP-40Pip was obtained.

[0083] The basic properties of the grafted flexible side chain cationic group containing sulfide flexible spacer anion exchange membranes obtained in Examples 1-4 above are shown in Table 1.

[0084] Table 1

[0085]

[0086] In the table: Test conditions: temperature is 80°C,

[0087] IEC t Theoretical value;

[0088] IEC e Measured by titration;

[0089] σMeasured by electrochemical workstation in pure water;

[0090] WU% is the change in mass before and after the membrane absorbs water;

[0091] SR% is the change in length before and after the membrane absorbs water.

[0092] As can be seen from Table 1, the IEC value of the PPSP-xPip anion exchange membrane prepared by the present application measured by molar titration is in the range of 1.47 to 2.15 mmol / g and close to the theoretical value. The higher the grafting rate, the higher the content of long side chain piperidine ion group per unit mass, and the larger the IEC value. The water absorption and swelling rate of the membrane increase with the increase of IEC and temperature: at 80°C, the water absorption of the membrane increases from 21.5% to 100.3%, and the swelling rate increases from 8.7% to 35.3%.

[0093] Meanwhile, the grafting ratio of PPSP-40Pip in Table 1 is too high, and the water absorption and swelling ratio are too large, which induces ion dilution, resulting in the decrease of the dimensional stability and ion conductivity of the membrane. Therefore, although PPSP-40Pip has an ideal water absorption compared with other membranes, the performance of the membrane is still weak due to the plasticizing and diluting effects of water molecules.

[0094] The ion conductivity of the anion exchange membrane is one of the key factors for evaluating the performance of the membrane. The ion conductivity of the PPSP-xPip anion exchange membrane was tested by the four-electrode method at a temperature range of 20°C to 80°C. As shown in Figure 5 , the ion conductivity of the anion exchange membrane increases with the increase of the temperature. For example, when the temperature increases from 20°C to 80°C, the hydroxyl ion conductivity of PPSP-35Pip increases from 44.08 mS cm -1 to 117.05 mS cm -1 . This is because the increase of the temperature provides the energy of thermal motion for the molecules, which accelerates the molecular motion, and on the other hand, the volume expansion of the polymer membrane increases the molecular motion space. At the same time, the ion conductivity of the membrane increases with the increase of the grafting ratio of the polymer, because the introduction of the ion group increases the IEC value and the water absorption of the membrane.

[0095] When the anion exchange membrane is assembled in the water electrolysis cell, the alkali resistance stability is one of the key performance indicators for evaluating the performance of the anion exchange membrane, because the strong alkaline hydroxyl ions are generated in the electrolysis process. In this test, the PPSP-35Pip anion exchange membrane was immersed in a 2 mol L -1 NaOH solution at 80°C for 520h. The alkali resistance stability of the anion exchange membrane was evaluated by measuring the ion conductivity of the anion exchange membrane. As shown in Figure 6 , the ion conductivity decreases with the increase of the time, and the retention rate is 98.05% after 520h.

[0096] Figure 7 The battery voltage durability curve is shown, and the steady-state polarization curve was recorded at 30°C under a constant current density of 500 mA cm -2 . During the whole test process, the voltage fluctuates between 1.87V and 1.89V, and the voltage retention rate is 98.93%. The overall test can verify the feasibility of the operation of the anion exchange membrane in alkaline conditions.

[0097] Having described various embodiments of the application, it is to be understood that the above description is meant not to be exhaustive or limited by the various embodiments disclosed. Many modifications and variations are possible in light of the above teachings without departing from the scope and spirit of the disclosed embodiments. It is therefore to be understood that within the scope of the claims and their equivalents, the application can be practiced otherwise than as specifically described.

Claims

1. A method of synthesis of grafted flexible side chain cationic group sulfide-ether flexible spacer anion exchange membrane material characterized by, The molecular structure of the anion exchange membrane material is shown as formula 1: Formula 1 The formula 1 is divided into a flexible side chain functionalized structural unit and a non-functionalized structural unit, the content of the flexible side chain functionalized structural unit x = 0.25-0.40; the content of the non-functionalized structural unit 1-x = 0.60-0.75; n = 350-1000, Wherein, the specific steps of the synthesis method are as follows: step A. Preparation of flexible spacer polyphenylene sulfide piperidine polymer containing sulfide: phenyl sulfide, 1-methyl-4-piperidone and dichloromethane are added to a three-necked flask, stirred under ice bath conditions, trifluoromethanesulfonic acid is added, and the reaction is continued under ice bath conditions, then the ice bath is removed, and the reaction is continued at room temperature. Diluted with dichloromethane, precipitated in alkaline solution to obtain white fine strip solid, the solid is separated out and washed with deionized water several times until neutral, dried to obtain flexible spacer polyphenylene sulfide piperidine polymer containing sulfide; Step B. Preparation of 6-bromohexyl-1-methylpiperidine bromide: a three-necked flask equipped with a stirrer, N2 inlet and outlet is added with 1,6-dibromohexane and ethyl acetate, heated and stirred, then a mixture of 1-methylpiperidine and ethyl acetate is added dropwise into the three-necked flask through a constant pressure funnel, and the mixture is further stirred, after the reaction is completed, the product is filtered and washed with ethyl acetate several times, then dried to obtain white solid powder 6-bromohexyl-1-methylpiperidine bromide; Step C. Preparation of flexible spacer anion exchange membrane material grafted with flexible side chain cationic group containing sulfide: the sulfide flexible spacer polyphenylene sulfide piperidine polymer prepared in step A and N-methyl pyrrolidone are added to a three-necked flask with nitrogen inlet and outlet, heated and stirred, after the polymer is completely dissolved, K2CO3 is added first, then 6-bromohexyl-1-methylpiperidine bromide prepared in step B is added, after the reaction is completed, the reaction solution is filtered through a G4 sand core funnel and poured into a prepared membrane container, dried to obtain flexible spacer anion exchange membrane grafted with flexible side chain cationic group containing sulfide.

2. The method of synthesis of grafted flexible side chain cationic group sulfur-ether containing flexible spacer anion exchange membrane material as claimed in claim 1 wherein, In step A, the molar ratio of diphenyl sulfide and 1-methyl-4-piperidone is 1:1-1:1.

3.

3. The method of synthesis of grafted flexible side chain cationic group sulfur-ether containing flexible spacer anion exchange membrane material as claimed in claim 1 wherein, In step A, the molar ratio of trifluoromethanesulfonic acid and 1-methyl-4-piperidone is 3:1-4:

1.

4. The method of synthesis of grafted flexible side chain cationic group sulfur-ether containing flexible spacer anion exchange membrane material as claimed in claim 1, wherein, In step B, the amount of 1,6-dibromohexane is 3-5 times that of 1-methylpiperidine, the reaction temperature is 40-60℃, and the reaction time is 6-12h.

5. The method of synthesis of grafted flexible side chain cationic group sulfur-ether flexible spacer anion exchange membrane material as claimed in claim 1 wherein, In step C, the amount of N-methyl pyrrolidone is 30-60 times the mass of the flexible spacer polyphenylene sulfide piperidine polymer containing sulfide. ​ 6. The method of synthesis of grafted flexible side chain cationic group sulfur-ether containing flexible spacer anion exchange membrane material as claimed in claim 1, wherein, In step C, the molar ratio of K2CO3 to flexible spacer polyphenylene sulfide piperidine polymer containing sulfide is 1:

1.

7. The method of synthesis of grafted flexible side chain cationic group sulfur-ether containing flexible spacer anion exchange membrane material as claimed in claim 1, wherein, In step C, the molar ratio of 6-bromohexyl-1-methylpiperidine bromide to flexible spacer polyphenylene sulfide piperidine polymer containing sulfide is 0.25:1-0.4:

1.

8. Use of anion exchange membrane material prepared by the method of synthesis of grafted flexible side chain cationic group sulfur-containing thioether flexible spacer anion exchange membrane material according to claim 1, characterized by The flexible spacer anion exchange membrane material grafted with flexible side chain cationic group containing sulfide can be applied as a key component in alkaline water electrolysis cell.

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