A method for preparing quinine type anion exchange membranes by pre-irradiation grafting

Abstract

The application belongs to the technical field of anion exchange membranes, and discloses a method for preparing a quinine type anion exchange membrane through pre-irradiation grafting. Linear carbon chain polymer is used as a base material, and a vinyl monomer is used as a grafting monomer. The linear carbon chain polymer is pre-irradiated by an electron beam radiation source, then the pre-irradiated base material is subjected to a grafting reaction in a vinyl monomer solution, and then the obtained grafted polymer is subjected to a quaternary ammonium reaction with a quinine ring solution, so as to obtain a quinine type anion exchange membrane. The overall process is relatively simple, the reaction conditions are mild, the reaction time is relatively short, and the cost is relatively low. The prepared quinine type anion exchange membrane has higher anion conductivity and better mechanical strength compared with a biphenyl quinine anion exchange membrane. The prepared quinine type anion exchange membrane has stronger chemical stability compared with a piperidine type and a trimethylamine type anion exchange membrane, so that it can be applied to the fields of fuel cells, water electrolysis, and flow batteries.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of anion exchange membranes, and particularly relates to a method for preparing an anion exchange membrane by irradiation grafting technology. BACKGROUND

[0002] An anion exchange membrane is widely used in hydrogen production by water electrolysis and fuel cells. The anion exchange membrane not only serves as a channel for hydrogen and oxygen ion exchange, but also prevents hydrogen and oxygen from contacting each other as a barrier, and provides support for the catalyst coating. Therefore, the anion exchange membrane needs to have extremely high ion conductivity and air tightness, as well as good chemical stability and mechanical stability. The performance of the anion exchange membrane directly affects the operation efficiency and service life of the anion exchange membrane water electrolysis hydrogen production and the anion exchange membrane fuel cell.

[0003] Irradiation grafting technology is one of the effective means to develop new materials with excellent performance or to modify the original materials by irradiation. The basic principle of irradiation grafting copolymerization is to use high-energy radiation to produce a number of active sites on the polymer backbone, and then successfully graft another vinyl monomer or homopolymer onto these active sites to produce a branched chain. The main advantages include: the irradiation grafting method is easier to master, operate and control than the general chemical grafting method; the irradiation grafting reaction can control the grafting rate according to the needs, such as the radiation dose; the irradiation grafting reaction is initiated by radiation, and no initiator needs to be added to the grafting system, so a very pure grafted polymer can be obtained. Irradiation grafting method can be divided into co-irradiation method and pre-irradiation method. Among them, the pre-irradiation grafting method does not need to purchase expensive radiation sources because the irradiation and grafting are two independent processes, so it is economically applicable. In short, the irradiation grafting method has been proven to be an economical and efficient technology for synthesizing anion exchange membranes due to its wide range of raw materials, low price, easy operation and flexible control of membrane modification. Irradiation grafting technology has been used by researchers to prepare anion exchange membranes, but the main grafting monomer is benzyltrimethylamine ion, which has insufficient overall alkaline stability, and high water absorption and swelling are the main factors restricting its wide application.

[0004] The polyaryl piperidine anion exchange membrane and its derivatives developed in 2018 have become the mainstream of anion exchange membrane research because of the relatively simple preparation method, mature preparation process, and high alkaline stability. In the past two years, the alkaline stability of the polyaryl quinine anion exchange membrane has been further improved. However, the use of super strong acid in the polymerization process limits the reaction conditions and further increases the risk of industrial production. In addition, polyaryl piperidine and its derivatives have high water absorption and low flexibility. In order to increase their practical value, fluoroketone monomers need to be introduced to improve their mechanical properties, but the high price of fluoroketone monomers hinders their commercial application prospects.

[0005] In summary, the mainstream polyaryl piperidine and its derivatives anion exchange membrane on the market still has many defects, can not meet the market application demand. Irradiation grafting preparation of anion exchange membrane due to its high conductivity, simple and controllable preparation method, low cost and other advantages become an effective means of large-scale preparation of anion exchange membrane. Further improve the alkaline stability of irradiation grafting anion exchange membrane to meet the high efficiency and long life of anion exchange membrane water electrolysis and anion exchange membrane fuel cell is the key problem to be solved in the field. SUMMARY

[0006] The purpose of the present application is to provide a method for preparing quinine type anion exchange membrane by pre-irradiation grafting technology. The prepared anion exchange membrane has high ionic conductivity, high chemical stability, high performance and strong stability in anion exchange membrane water electrolysis and anion exchange membrane fuel cell.

[0007] In order to solve the above technical problems, the present application is realized by the following technical scheme:

[0008] According to one aspect of the present application, a method for preparing quinine type anion exchange membrane by pre-irradiation grafting is provided, in which a linear carbon chain polymer is used as a substrate, a vinyl monomer is used as a grafting monomer, the linear carbon chain polymer is pre-irradiated by an electron beam radiation source, then the pre-irradiated substrate is subjected to grafting reaction in a vinyl monomer solution, and the obtained grafting polymer is subjected to quaternary ammonium reaction with a quinine ring solution, thereby obtaining a quinine type anion exchange membrane.

[0009] Further, the linear carbon chain polymer is at least one of ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), fluorinated ethylene propylene copolymer (FEP), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), hydrogenated styrene-butadiene block copolymer (SEBS).

[0010] Further, the vinyl monomer is at least one of vinyl benzyl chloride, chloromethyl styrene, bromo undecene, bromo octadecene.

[0011] Further, the concentration of the vinyl monomer solution is 5wt%-20wt%, and the solvent of the vinyl monomer solution is at least one of water, isopropyl alcohol, toluene, benzene, N-methyl-2-pyrrolidone.

[0012] Further, the irradiation energy of the pre-irradiation is 4.5MeV-10MeV, and the total dose is 30kGy-150kGy.

[0013] Further, the vinyl monomer solution includes a solvent in an amount of 2-9 times the volume of the vinyl monomer, the solvent being at least one of water, isopropyl alcohol, toluene, benzene, and N-methyl-2-pyrrolidone.

[0014] Further, the vinyl monomer solution includes a surfactant in an amount of 10%-50% of the volume of the vinyl monomer.

[0015] Further, the concentration of the quinuclidine solution is 3wt%-10wt%.

[0016] Further, the method includes the following steps:

[0017] (1) The linear carbon chain polymer is subjected to electron beam irradiation in air or an inert gas at ≤1 atmosphere; the irradiated substrate is stored at a temperature of ≤-40°C;

[0018] (2) After the vinyl monomer solution in the reactor is deoxygenated by passing an inert gas, the vinyl monomer solution is put into the substrate obtained in step (1), and the inert gas is continuously fed into the solution system to exhaust oxygen;

[0019] (3) After the reactor is sealed, grafting reaction is carried out by constant temperature heating to prepare the grafted linear carbon chain polymer, the constant temperature heating temperature is 40°C-80°C, and the time is 4h-16h;

[0020] (4) The grafted linear carbon chain polymer is cleaned in a solvent, and after cleaning, it is dried in a vacuum drying oven at 50°C-80°C;

[0021] (5) The cleaned and dried grafted linear carbon chain polymer is placed in a quinuclidine solution for quaternization reaction at 70°C-85°C for 5 days-7 days;

[0022] (6) After the quaternization reaction, the substrate is washed with water and then placed in a NaCl or NaOH solution at room temperature for ion exchange to obtain a quinuclidine type anion exchange membrane.

[0023] Further, the solvent in step (4) is at least one of water, isopropyl alcohol, toluene, ethanol, and methanol.

[0024] According to another aspect of the present application, a quinuclidine type anion exchange membrane prepared by pre-irradiation grafting is provided.

[0025] The present application has the following advantages:

[0026] The application grafts quinuclidine functional groups on the linear carbon chain polymer skeleton through the pre-irradiation grafting technology, so that the linear carbon chain polymer has anion exchange function, the method has relatively simple overall process, mild reaction condition, shorter reaction time and lower cost; the prepared quinuclidine type anion exchange membrane has higher anion conductivity and better mechanical flexibility compared with the biphenyl quinuclidine anion exchange membrane, and has stronger chemical stability compared with the piperidine type and trimethylamine type anion exchange membranes, so that the quinuclidine type anion exchange membrane can be applied to the fields of fuel cells, water electrolysis, flow batteries and the like. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 Reaction equation of the ETFE-based quinuclidine type anion exchange membrane prepared in Example 1;

[0028] Figure 2 Hydroxyl ion conductivity of the ETFE-based quinuclidine type anion exchange membrane prepared in Example 1;

[0029] Figure 3 LSV curve of the ETFE-based quinuclidine type anion exchange membrane prepared in Example 1 in an alkaline electrolytic cell at 60 DEG C and 80 DEG C;

[0030] Figure 4 EIS curve of the ETFE-based quinuclidine type anion exchange membrane prepared in Example 1 in an alkaline electrolytic cell at 60 DEG C and 80 DEG C. DETAILED DESCRIPTION

[0031] The application provides a quinuclidine type anion exchange membrane prepared by pre-irradiation grafting and a method thereof, which uses a linear carbon chain polymer as a base material and a vinyl monomer as a grafting monomer, pre-irradiates the linear carbon chain polymer with an electron beam source, then performs grafting reaction on the pre-irradiated base material in a vinyl monomer solution, and then performs quaternary ammonium reaction on the obtained grafted polymer and a quinuclidine ring solution, so as to obtain the quinuclidine type anion exchange membrane.

[0032] Specifically, the method can include the following steps:

[0033] (1) performing electron beam irradiation on the linear carbon chain polymer in air or inert gas at ≤1 atmosphere; and storing the irradiated base material at ≤-40 DEG C;

[0034] (2) after removing oxygen from the vinyl monomer solution in the reactor by inert gas, putting the vinyl monomer solution into the base material obtained in step (1), and continuously filling the inert gas into the solution system to exhaust oxygen;

[0035] (3) sealing the reactor and performing grafting reaction to prepare grafted linear carbon chain polymer by constant temperature heating, wherein the constant temperature heating temperature is 40 DEG C-80 DEG C, and the constant temperature heating time is 4h-16h;

[0036] (4) the grafted linear carbon chain polymer is cleaned in a solvent, and after cleaning, is dried in a vacuum drying oven at 50-80°C; wherein the solvent is at least one of water, isopropyl alcohol, toluene, ethanol, and methanol;

[0037] (5) the grafted linear carbon chain polymer after cleaning and drying is placed in a quinuclidine ring solution and subjected to a quaternary ammonium reaction at 70-85°C for 5-7 days;

[0038] (6) the substrate after the quaternary ammonium reaction is washed with water and then placed in a NaCl or NaOH solution at room temperature to perform ion exchange, thereby obtaining a quinuclidine type anion exchange membrane.

[0039] For some preferred embodiments of the present application, the linear carbon chain polymer is at least one of ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), fluorinated ethylene propylene copolymer (FEP), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), and hydrogenated styrene-butadiene block copolymer (SEBS).

[0040] For some preferred embodiments of the present application, the vinyl monomer is at least one of vinyl benzyl chloride, chloromethyl styrene, bromo undecene, and bromo octadecene.

[0041] For some preferred embodiments of the present application, the concentration of the vinyl monomer solution is 5-20 wt%.

[0042] For some preferred embodiments of the present application, the irradiation energy of the pre-irradiation is 4.5-10 MeV, and the total dose is 30-150 kGy.

[0043] For some preferred embodiments of the present application, the vinyl monomer solution includes 10-50% of a surfactant by volume of the vinyl monomer.

[0044] For some preferred embodiments of the present application, the concentration of the quinuclidine ring solution is 3-10 wt%.

[0045] The specific embodiments of the present application are described in more detail below with reference to the accompanying drawings and examples, so that the advantages of the present application and its various aspects can be better understood. It should be noted that the following specific embodiments and examples are for illustrative purposes only, and are not limiting of the present application.

[0046] Example 1

[0047] This embodiment provides a preparation method of an ETFE-based quinuclidine type anion exchange membrane, and the specific structure is shown as follows:

[0048]

[0049] And, the following steps are taken:

[0050] 1) The ETFE base film is subjected to electron beam irradiation in air at < 1 atmosphere; the irradiation energy is 10 MeV and the total dose is 100 kGy;

[0051] 2) The irradiated ETFE base film is stored at -40°C;

[0052] 3) 5 ml of vinylbenzyl chloride monomer, 1 ml of N-octyl pyrrolidone, and 94 ml of deionized water are added to a Schlenk tube to form a grafting monomer solution, and argon is bubbled for 30 minutes to remove oxygen;

[0053] 4) The irradiated and frozen-stored ETFE base film is placed in the grafting monomer solution, and argon is continued to be bubbled for 2 hours to exhaust oxygen;

[0054] 5) After the Schlenk tube is sealed, magnetic stirring is performed under an argon atmosphere, and the temperature is raised to 70°C for grafting reaction for 16 hours;

[0055] 6) After the grafting reaction is completed, the film turns light yellow, and it is washed in isopropyl alcohol for 1 hour and vacuum dried at 70°C for 5 hours;

[0056] 7) The grafted ETFE base film is placed in a 120 ml NMP solution containing 5 g of quinuclidine, and a quaternary ammonium reaction is performed at 80°C for 5 days;

[0057] 8) The quaternary ammonium-treated ETFE base film is placed in a 1M sodium chloride solution for ion exchange for 24 hours;

[0058] 9) The ion-exchanged quinuclidine anion exchange film is washed in deionized water.

[0059] Figure 1 The reaction equation for the ETFE base quinuclidine anion exchange film prepared in this example is shown below, Figure 1 which shows that this example is performed in three steps of irradiation, grafting, and functionalization.

[0060] Figure 2 The hydroxyl ion conductivity of the ETFE base quinuclidine anion exchange film prepared in this example is tested by the alternating current impedance method in the range of 1-10 5 Hz on the anion exchange film material, and the ohmic resistance generated is recorded as R. The conductivity of the sample to be tested can be calculated by the formula:

[0061] σ = L / (A·R)

[0062] Wherein, the thickness of the sample to be measured is denoted as L, and the unit is cm; the contact area of the anion exchange membrane and the electrode is denoted as A, and the unit is cm 2 .

[0063] By Figure 2 It can be seen that the ETFE-based quinine-type anion exchange membrane prepared in Example 1 has a conductivity higher than 75 mS / cm at room temperature and a conductivity higher than 150 mS / cm at 80℃. The high conductivity of the anion exchange membrane indicates its good application prospect.

[0064] The anion exchange membrane prepared in Example 1 was assembled into a membrane electrode with a 4 cm 2 size IrO2 electrode and Pt / C electrode, and installed in an electrolytic cell. The electrolyte solution was 1M KOH solution, and a linear voltammetry scan test was performed using an electrochemical workstation. The results are shown in Figure 3 From Figure 3 it can be seen that the voltage of the (membrane electrode) at 1A / cm 2 at 60℃ is only 1.64V, and the voltage at 1A / cm 2 at 80℃ is only 1.64V, which shows that the membrane electrode prepared with the quinine-type anion exchange membrane has excellent water electrolysis performance.

[0065] Subsequently, the two-electrode method was used to test the alternating current impedance of the membrane electrode prepared with the quinine-type anion exchange membrane at 1A / cm 2 , and Figure 4 the EIS curve of the membrane electrode at 60℃ and 80℃ was plotted. It can be seen that the electrochemical impedance at 60℃ is only 0.062Ω, and the electrochemical impedance at 80℃ is only 0.051Ω, which indicates that the membrane electrode prepared with the irradiation grafted quinine-type anion exchange membrane has a lower electrochemical impedance performance.

[0066] Example 2

[0067] The present embodiment provides a preparation method of an ETFE-based quinine-type anion exchange membrane, which is performed according to the following steps:

[0068] 1) Electron beam irradiation of the ETFE-based membrane in air at ≤1 atmosphere; the irradiation energy is 10 MeV, and the total dose is 20 kGy;

[0069] 2) Storage of the irradiated ETFE-based membrane at -80℃;

[0070] 3) In a Schlenk tube, 10 ml of vinylbenzyl chloride monomer, 1 ml of N-octyl pyrrolidone, and 80 ml of deionized water are added to form a grafting monomer solution, and argon is introduced for 30 minutes to remove oxygen;

[0071] 4) The irradiated and frozen-stored ETFE-based membrane was put into the grafting monomer solution, and argon was continuously bubbled for 1 hour to remove oxygen;

[0072] 5) After the Schlenk tube was sealed, magnetic stirring was performed under an argon atmosphere, and the temperature was raised to 60°C for grafting reaction for 1 hour;

[0073] 6) After the grafting reaction was completed, the membrane turned light yellow, and was washed in isopropanol for 1 hour and vacuum dried at 50°C for 16 hours;

[0074] 7) The grafted ETFE-based membrane was put into a 100ml NMP solution containing 8g quinuclidine, and the quaternization reaction was performed at 60°C for 3 days;

[0075] 8) The quaternized ETFE-based membrane was put into a 1M sodium hydroxide solution for ion exchange for 24 hours;

[0076] 9) The ion-exchanged quinuclidine anion exchange membrane was washed in deionized water.

[0077] Example 3

[0078] This example provides a preparation method of an HDPE-based quinuclidine anion exchange membrane, and the specific structure is as follows:

[0079] And, the following steps were performed:

[0080]

[0081] 1) The HDPE-based membrane was subjected to electron beam irradiation in air at ≤1 atmosphere; the irradiation energy was 4.5MeV, and the total dose was 150kGy;

[0082] 2) The irradiated HDPE-based membrane was stored at -80°C;

[0083] 3) 10ml of vinylbenzyl chloride monomer, 1ml of N-octyl pyrrolidone, and 80ml of deionized water were added to a Schlenk tube to form a grafting monomer solution, and argon was bubbled for 30 minutes to remove oxygen;

[0084] 4) The irradiated and frozen-stored HDPE-based membrane was put into the grafting monomer solution, and argon was continuously bubbled for 2 hours to remove oxygen;

[0085] 5) After the Schlenk tube was sealed, magnetic stirring was performed under an argon atmosphere, and the temperature was raised to 60°C for grafting reaction for 4 hours;

[0086] 6) After the grafting reaction was completed, the membrane turned white, and was washed in isopropanol for 1 hour and vacuum dried at 50°C for 5 hours;

[0087] 7) The grafted PVDF based membrane was put into 8g quinuclidine in 120ml NMP solution and quaternization reaction was carried out at 80°C for 5 days;

[0088] 8) The quaternized PVDF based membrane was put into 1M sodium chloride solution for ion exchange for 24 hours;

[0089] 9) The ion exchanged quinuclidine type anion exchange membrane was put into deionized water for washing.

[0090] Example 4

[0091] This example provides a preparation method of PVDF based quinuclidine type anion exchange membrane, the specific structure is as shown below: and according to the following steps:

[0092]

[0093] 1) The PVDF based membrane was subjected to electron beam irradiation in air at ≤1 atmosphere; the irradiation energy was 10MeV, and the total dose was 30kGy;

[0094] 2) The irradiated PVDF based membrane was stored at -40°C;

[0095] 3) 20ml of vinylbenzyl chloride monomer, 1ml of N-octyl pyrrolidone, and 79ml of isopropyl alcohol were added to a Schlenk tube to form a grafting monomer solution, and argon was introduced for 30 minutes to remove oxygen;

[0096] 4) The irradiated PVDF based membrane was put into the grafting monomer solution, and argon was continuously introduced for 2 hours to exhaust oxygen;

[0097] 5) After the Schlenk tube was sealed, magnetic stirring was carried out under nitrogen atmosphere, and the temperature was raised to 70°C for grafting reaction for 8h;

[0098] 6) After the grafting reaction was completed, the membrane was washed in toluene for 1 hour, and vacuum dried at 70°C for 4 hours;

[0099] 7) The grafted PVDF based membrane was put into 8g quinuclidine in 120ml NMP solution and quaternization reaction was carried out at 80°C for 5 days;

[0100] 8) The quaternized PVDF based membrane was put into 1M sodium chloride solution for ion exchange for 24 hours;

[0101] 9) The ion exchanged quinuclidine type anion exchange membrane was put into deionized water for washing.

[0102] Comparative Example 1

[0103] The embodiment provides a preparation method of an ETFE-based piperidine anion exchange membrane, and is performed according to the following steps:

[0104] 1) Electron beam irradiation of the ETFE-based membrane in air at <=1 atm; irradiation energy is 4.5 MeV, and the total dose is 100 kGy;

[0105] 2) Storage of the irradiated ETFE-based membrane in -40 DEG C;

[0106] 3) 5 ml of vinyl benzyl chloride monomer, 1 ml of N-octyl pyrrolidone and 94 ml of deionized water are added into a Schlenk tube to prepare a grafting monomer solution, and argon is introduced for 30 minutes to remove oxygen;

[0107] 4) The irradiated ETFE-based membrane is placed into the grafting monomer solution, and argon is continuously introduced for 2 hours to exhaust oxygen;

[0108] 5) After the Schlenk tube is sealed, the grafting reaction is performed under a nitrogen atmosphere and under magnetic stirring, and the temperature is increased to 70 DEG C for 16 hours;

[0109] 6) After the grafting reaction is completed, the grafting membrane is washed in isopropyl alcohol for 1 hour, and vacuum drying is performed at 70 DEG C for 5 hours;

[0110] 7) The grafted ETFE-based membrane is placed into 200 ml of NMP solution containing 10 g of N-methyl piperidine, and quaternization reaction is performed at 80 DEG C for 7 days;

[0111] 8) The quaternary ammonium membrane is placed into a 1M sodium chloride solution for ion exchange for 24 hours;

[0112] 9) The ion-exchanged quinine anion exchange membrane is washed in deionized water

[0113] The ETFE-based piperidine anion exchange membrane prepared by pre-irradiation grafting in the above embodiment and the comparative example is subjected to water absorption rate, water absorption swelling, ion exchange capacity and hydroxyl ion conductivity tests, and specific data are shown in the following table:

[0114]

[0115]

[0116] The above examples and comparative examples synthesize anion exchange membranes based on pre-irradiation grafting with different main chain structures and functional groups. As can be seen from the table, Example 1 and Example 2 have obvious differences in radiation intensity and grafting conditions, thereby affecting the performance of the anion exchange membrane. By controlling the irradiation intensity, the number of free radicals can be changed. By controlling the grafting conditions, the number and length of the side chains can be changed, so as to change the overall performance of the anion exchange membrane. The difference between Example 1 and Comparative Example 1 lies in the difference of the functional groups. The alkaline stability of the quinine type anion exchange membrane is obviously better than that of the piperidine type anion exchange membrane, and the conductivity is higher than that of the piperidine type anion exchange membrane. Example 1, Example 3 and Example 4 select different main chain structures and have different grafting conditions, resulting in differences in the performance of the finally formed anion exchange membrane. This proves that different carbon chain polymers can be selected according to the different application scenarios of the anion exchange membrane, and the preparation method of the quinine type anion exchange membrane of the present application is applicable to different linear carbon chain polymers. In addition, the anion exchange membranes synthesized by the present application all have high conductivity and strong flexibility. Among them, Example 1 and Example 3 exhibit high hydroxyl ion conductivity (> 145 mS / cm) and good flexibility (elongation at break > 75%).

[0117] Although the preferred embodiments of the present application are described above in conjunction with the drawings, the present application is not limited to the above specific embodiments, and the above specific embodiments are only illustrative and not restrictive. Those skilled in the art can make many specific changes to the embodiments under the guidance of the present application without departing from the spirit and scope of the present application and the scope of protection of the claims.

Claims

1. A method for preparing a quinine-type anion exchange membrane by pre-irradiation grafting, characterized by, The linear carbon chain polymer is used as a substrate, a vinyl monomer is used as a grafting monomer, the linear carbon chain polymer is pre-irradiated by an electron beam source, then the pre-irradiated substrate is grafted in a vinyl monomer solution, and then the obtained grafted polymer is subjected to a quaternization reaction with a quinuclidine solution, so as to obtain a quinuclidine type anion exchange membrane.

2. The method of claim 1, wherein the pre-irradiation grafting is performed by irradiating the quaternary ammonium salt-containing polymer with an electron beam having an energy of 1 to 10 MeV at a dose of 5 to 100 Mrad. The linear carbon chain polymer is at least one of ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), fluorinated ethylene propylene copolymer (FEP), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), hydrogenated styrene-butadiene block copolymer (SEBS).

3. The method of claim 1, wherein the pre-irradiation grafting is performed by irradiating the quaternary ammonium salt-containing polymer with an electron beam having an energy of 1 to 10 MeV at a dose of 5 to 100 Mrad. The vinyl monomer is at least one of vinyl benzyl chloride, chloromethyl styrene, bromo undecene, bromo octadecene.

4. The method of claim 1, wherein the pre-irradiation grafting is performed by irradiating the quaternary ammonium salt-containing polymer with an electron beam having an energy of 1 to 10 MeV at a dose of 5 to 100 Mrad. The concentration of the vinyl monomer solution is 5 wt% to 20 wt%, and the solvent of the vinyl monomer solution is at least one of water, isopropyl alcohol, toluene, benzene, N-methyl-2-pyrrolidone.

5. The method of claim 1, wherein the pre-irradiation grafting is performed by irradiating the quaternary ammonium salt-containing polymer with an electron beam having an energy of 1 to 10 MeV at a dose of 5 to 50 Mrad. The irradiation energy of the pre-irradiation is 4.5 MeV to 10 MeV, and the total dose is 30 kGy to 150 kGy.

6. The method of claim 1, wherein the pre-irradiation grafting is performed by irradiating the quaternary ammonium salt-containing polymer with an electron beam having an energy of 1 to 10 MeV. The vinyl monomer solution includes a surfactant accounting for 10% to 50% of the volume of the vinyl monomer.

7. The method of claim 1, wherein the pre-irradiation grafting is performed by irradiating the quaternary ammonium salt-containing polymer with an electron beam having an energy of 1 to 10 MeV at a dose of 5 to 100 Mrad. The concentration of the quinuclidine solution is 3 wt% to 10 wt%.

8. A method of preparing a quaternary anion exchange membrane by means of pre- irradiation grafting according to any one of claims 1 to 7, characterized in that, The method comprises the following steps: (1) The linear carbon chain polymer is subjected to electron beam irradiation in air or inert gas at ≤1 atmosphere; the irradiated substrate is stored at a temperature of ≤-40°C; (2) After the vinyl monomer solution in the reactor is deoxygenated by inert gas, the vinyl monomer solution is put into the substrate obtained in step (1), and inert gas is continuously filled into the solution system to exhaust oxygen; (3) After the reactor is sealed, grafting reaction is carried out by constant temperature heating to prepare grafted linear carbon chain polymer, the temperature of constant temperature heating is 40°C to 80°C, and the time is 4 h to 16 h; (4) The grafted linear carbon chain polymer is cleaned in a solvent, and then dried in a vacuum drying box at 50°C to 80°C; (5) The cleaned and dried grafted linear carbon chain polymer is placed in a quinuclidine solution for quaternization reaction at 70°C to 85°C for 5 days to 7 days; (6) After the quaternization reaction, the substrate is washed with water and then placed in a NaCl or NaOH solution at room temperature for ion exchange, so as to obtain a quinuclidine type anion exchange membrane.

9. The method of claim 8, wherein the pre-irradiation grafting is performed by irradiating the quaternary ammonium salt-containing polymer with an electron beam having an energy of 1 to 10 MeV at a dose of 5 to 50 Mrad. The solvent in step (4) is at least one of water, isopropyl alcohol, toluene, ethanol, and methanol.

10. A pre-irradiation grafted quaternary anion exchange membrane prepared by the process comprising the steps of: Prepared by the method of any one of claims 1-9.

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