CN111793156A - Block anion exchange membrane and preparation method thereof - Google Patents
Block anion exchange membrane and preparation method thereof Download PDFInfo
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- CN111793156A CN111793156A CN202010723047.6A CN202010723047A CN111793156A CN 111793156 A CN111793156 A CN 111793156A CN 202010723047 A CN202010723047 A CN 202010723047A CN 111793156 A CN111793156 A CN 111793156A
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Abstract
The invention provides a block anion exchange membrane and a preparation method thereof. The preparation method comprises the following steps: synthesizing a first-stage polymer by initiating polymerization by adopting visible light by using 2-bromoethyl acrylate as a first monomer and BTPA as a first chain transfer reagent; taking the first-stage polymer as a second chain transfer reagent and a styrene compound as a second monomer, and synthesizing a block polymer by initiating polymerization by adopting visible light; the block polymer reacts with a functional reagent containing pyrrole groups to prepare the block anion exchange membrane. The photo-initiated RAFT polymerization condition adopted by the invention is mild, the environment is friendly, the reaction is high-efficiency, the usage amount of the photocatalyst is less, the synthesized block polymer is easy to form a clear hydrophilic-hydrophobic microphase separation morphology due to the special soft-hard segment structure, the ion transmission efficiency is high, and the introduced pyrrole group endows the membrane with higher alkali-resistant stability. The method provides an efficient and mild way for preparing the anion exchange membrane with special configuration and excellent performance.
Description
Technical Field
The invention relates to the technical field of fuel cell membrane materials, in particular to a block anion exchange membrane and a preparation method thereof.
Background
As anion exchange membranes are increasingly widely used in electrochemical energy conversion and storage devices such as fuel cells, water electrolyzers and redox flow batteries, the development of high conductivity, high stability anion exchange membranes has become a current research hotspot. Among them, block polymers are particularly attracting attention because they can form oriented and continuous through-going hydrophilic/hydrophobic channels. The hydrophilic through region formed by the block polymer in the film forming process can provide a channel for the transmission of ions, thereby improving the ion transmission performance of the block polymer and obtaining high ion conductivity; the formed hydrophobic through-region can ensure the mechanical stability of the membrane.
Currently, the main methods for preparing block type anionic polymer backbones are: condensation polymerization between aryl halogens and phenolic hydroxyl groups, Ni-catalyzed coupling reactions, traditional living polymerization reactions such as Atom Transfer Radical Polymerization (ATRP), reversible addition-fragmentation chain transfer polymerization (RAFT), anionic polymerization, and ring-opening metathesis polymerization (ROMP), among others. Wherein, the temperature of the polycondensation reaction is as high as 170 ℃, and the feeding ratio of the monomers is strictly controlled to obtain the block polymer with high molecular weight; ATRP and RAFT polymerization also need to be carried out at high temperature, and the amount of catalyst needed by ATRP polymerization is large, so that the problem of metal residue exists; anionic polymerization needs to be carried out at temperatures as low as-80 ℃ and requires the use of the hazardous reagent butyl lithium; in addition to the use of large amounts of metal catalysts, ROMP greatly limits the structure of block polymers due to the limited range of monomers available. The above methods have the defects of requiring reaction at high temperature or very low temperature, being difficult to control the reaction process, and the like.
Disclosure of Invention
The invention solves the problems that the existing method for preparing the block type anionic polymer main chain has the defects of not mild reaction conditions, difficult control, metal residue or use of dangerous reagents and the like.
To solve at least one of the above problems, the present invention provides a method for preparing a block anion exchange membrane, comprising:
taking an acrylate compound containing a functional group precursor as a first monomer, taking 2- (butyl trithiocarbonate) propionic acid as a first chain transfer reagent, and synthesizing a first-stage polymer by adopting a visible light initiated RAFT (reversible addition-fragmentation chain transfer) polymerization method;
synthesizing a block polymer by using the first-stage polymer as a second chain transfer reagent and a styrene compound as a second monomer by adopting a visible light initiated RAFT (reversible addition-fragmentation chain transfer) polymerization method;
adding a functional reagent containing a pyrrole group, a trimethylamine group or a piperidine group into the organic solution of the block polymer, and carrying out quaternization reaction on the first-stage polymer and the pyrrole group, the trimethylamine group or the piperidine group to obtain a functional polymer;
and dissolving the functionalized polymer in a solvent to obtain a membrane casting solution, pouring the membrane casting solution on a substrate, and drying to obtain the block anion exchange membrane.
Preferably, the functional group-containing precursor includes a halogen group that can be functionalized.
Preferably, the first monomer is 2-bromoethyl acrylate.
Preferably, the functionalizing agent comprises one of 1-methylpyrrolidine, trimethylamine, and N-methylpiperidine.
Preferably, the second monomer comprises one of styrene, 4-fluorostyrene and pentafluorostyrene.
Preferably, the molar ratio of the first monomer to the second monomer is 1:2 to 3: 2.
Preferably, the synthesis process of the first stage polymer is as follows: adding the first chain transfer reagent into a first reaction tube, removing air in the first reaction tube by adopting a vacuumizing and argon circulating method, adding the first monomer and an organic solution of a photocatalyst into the first reaction tube to obtain a first reaction solution, placing the first reaction solution under visible light for irradiation at room temperature, reacting for 20-45min, and after the reaction is finished, diluting, precipitating, filtering and purifying the first reaction solution to obtain a first-stage polymer;
the synthesis process of the block polymer comprises the following steps: adding the first-stage polymer into the second reaction tube, removing air in the second reaction tube by adopting a vacuumizing and argon circulating method, adding the second monomer and the organic solution of the photocatalyst into the second reaction tube to obtain a second reaction solution, placing the second reaction solution under visible light for irradiation at room temperature, reacting for 60-180min, and after the reaction is finished, diluting, precipitating and purifying the second reaction solution to obtain the block polymer.
Preferably, the synthesis process of the functionalized polymer is as follows: adding the functional reagent into the organic solution of the block polymer, carrying out quaternization reaction in an oil bath kettle at the temperature of 80-90 ℃ under the stirring condition for 20-24h to obtain a third reaction liquid, dropwise adding the third reaction liquid into methanol under the stirring condition to precipitate a polymer, and purifying the polymer to obtain the functional polymer.
The invention also provides a block anion exchange membrane which is prepared by adopting the preparation method of the block anion exchange membrane.
The structural formula of the block anion exchange membrane prepared by the invention is as follows:
compared with the prior art, the block anion exchange membrane and the preparation method thereof provided by the invention have the following advantages:
according to the invention, visible light is adopted to initiate polymerization to synthesize a block polymer with a soft-hard segment structure, and a pyrrole group, a trimethylamine group or a piperidine group is introduced into the block polymer, so that the prepared block anion exchange membrane is easy to form a clear hydrophilic-hydrophobic microphase separation morphology, has high ion transmission efficiency, and simultaneously has high alkali resistance, heat resistance and swelling resistance stability, so that the block anion exchange membrane material prepared by the invention can simultaneously meet high conductivity and high alkali resistance stability.
In addition, the block type anion exchange membrane is synthesized by the photocatalysis method, the synthesis condition is mild, the synthesis can be carried out at room temperature, the operation is simple and convenient, the usage amount of the photocatalyst is small, the metal residue is small, the proportion of the soft segment and the hard segment can be controlled by controlling the feeding and reaction time, so that the phase separation morphology of the membrane is adjusted, and the defects that the reaction condition is not mild enough and is difficult to control, the metal residue exists or a dangerous reagent is used and the like in the existing preparation method are overcome.
Drawings
FIG. 1 is a flow chart of a method for preparing a block anion exchange membrane according to an embodiment of the present invention;
FIG. 2 is a TEM image of a block anion exchange membrane prepared in example 1 of the present invention;
FIG. 3 is a graph showing the change in mechanical strength and elongation at break of the block anion exchange membrane prepared in example 1 of the present invention;
FIG. 4 is a thermal decomposition profile of a block anion exchange membrane prepared in example 1 of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
The embodiment of the invention provides a preparation method of a block anion exchange membrane, which comprises the following steps:
s1, synthesizing a first-stage polymer by using an acrylate compound containing a functional group precursor as a first monomer, using 2- (butyltrithiocarbonate) propionic acid (BTPA) as a first chain transfer reagent and adopting a visible light initiated RAFT polymerization method;
s2, synthesizing a block polymer by using the first-stage polymer as a second chain transfer reagent and a styrene compound as a second monomer by adopting a visible light initiated RAFT polymerization method;
s3, obtaining an organic solution based on the block polymer, adding a functional reagent containing a pyrrole group, a trimethylamine group or a piperidine group into the organic solution of the block polymer, and carrying out quaternization reaction on a functional group precursor in the first-stage polymer and the pyrrole group, the trimethylamine group or the piperidine group to obtain a functional polymer;
and S4, dissolving the functional polymer in a solvent to obtain a membrane casting solution, pouring the membrane casting solution on a substrate, and drying to obtain the block anion exchange membrane.
In this example, a visible light-initiated RAFT polymerization method is first used to synthesize a block polymer, and in S1, the synthesis process of the first stage polymer is: adding a first chain transfer reagent into a first reaction tube, removing air in the first reaction tube by adopting a three-time vacuumizing and argon circulating method, adding a first monomer and an organic solution of a photocatalyst into the first reaction tube to obtain a first reaction liquid, and placing the first reaction liquid under the condition of room temperature and irradiating under visible light for reacting for 20-45 min. And after the reaction is finished, diluting, precipitating and purifying the first reaction solution to obtain a first-stage polymer. In S2, the synthesis process of the block polymer is as follows: adding a second chain transfer reagent into a second reaction tube, removing air in the second reaction tube by adopting a three-time vacuumizing and argon circulating method, adding a second monomer and an organic solution of a photocatalyst into the second reaction tube to obtain a second reaction liquid, placing the second reaction liquid under the condition of room temperature and irradiating under visible light for reacting for 60-180min, and after the reaction is finished, diluting, precipitating and purifying the second reaction liquid to obtain the block polymer.
And secondly, functionalizing the block polymer, in S3, adding a functionalizing reagent into an organic solution of the block polymer, carrying out quaternization reaction in an oil bath kettle at the temperature of 80-90 ℃ under stirring for 20-24h to obtain a third reaction solution, dropwise adding the third reaction solution into methanol under stirring to precipitate the polymer, and purifying the polymer to obtain a functionalized polymer, wherein the functionalized polymer contains ionic functional groups such as pyrrolidinium salt or quaternary ammonium salt.
Finally, preparing the block anion exchange membrane by adopting a tape casting membrane forming method.
The block type anion exchange membrane formed by polymerizing the first section polymer and the second section polymer has a special soft-hard section structure, the soft-hard section structure shows that a regular hydrophilic-hydrophobic phase separation appearance is easily formed in a membrane forming process, hydrophilic areas are communicated with each other to form a communicated hydrophilic channel, a smooth and unimpeded channel is provided for ion transmission, and the hydrophobic areas ensure the mechanical stability of the membrane.
The molar ratio of the first monomer to the second monomer is from 1:2 to 3:2, preferably 2: 3. The ratio of the soft segment to the hard segment in the block polymer is regulated and controlled by controlling the molar ratio of the first monomer to the second monomer, so that the phase separation morphology is regulated, and the performance of the membrane is improved.
In addition, two monomers participating in the synthesis of the block polymer are a first monomer acrylate compound and a second monomer styrene compound respectively, and the RAFT polymerization activity of the acrylate compound is greater than that of the styrene compound, so that the first-stage polymer in S2 can be used as a chain transfer reagent to initiate a second-stage continuous polymerization, and the block polymer is finally formed.
Further, the functional group-containing precursor in the first monomer is suitable for performing a quaternization reaction with a subsequent functionalizing agent to obtain an ionic functional group, where the functional group-containing precursor includes a halogen group, and the halogen group is preferably bromine in this embodiment.
The second monomer is a styrene compound, can be styrene, and can also be a styrene compound containing a second functional group, wherein the second functional group is preferably a group capable of promoting the microphase separation of the block polymer. Since fluorine atoms can improve the performance of the film, chemical stability of the film, resistance to water swelling, and the like, the second functional group in this embodiment is preferably a fluorine atom, and in some embodiments, the second monomer is preferably pentafluorostyrene.
Further, the functionalizing agent comprises one of 1-methylpyrrolidine, trimethylamine and N-methylpiperidine.
Further, when visible light is used to initiate polymerization, the chain transfer reagent, the monomer and the photocatalyst are matched with each other to initiate polymerization, in this embodiment, the first monomer is an acrylate compound, the first chain transfer reagent is BTPA, and the synthesis process is as follows: 32.00g (16.00g,400mmol NaOH) of 50% NaOH aqueous solution was added to a mixture of 36.0g (400mmol) of butanethiol and 60mL of water with stirring, followed by 20mL of acetone to give a clear, colorless solution, which was cooled to room temperature after stirring for 0.5 h. Carbon disulfide (27 mL, 34.2g,450mmol) was added to give a clear orange solution, and the reaction was stirred for 0.5h and then cooled to below 10 ℃ in an ice bath. 62.73g (410mmol) of 2-bromopropionic acid were added slowly so that the temperature was always below 30 ℃ and then 32.80g (410mmol) of 50% aqueous NaOH solution were added slowly so that the temperature did not exceed 30 ℃. After the exotherm ceased, the ice bath was removed, 60mL of water was added and the mixture was stirred at ambient temperature for 24 h. The reaction was diluted with 100mL of water, stirred, cooled in an ice bath, and 60mL of 10M HCl was added slowly to bring the reaction temperature below 10 ℃. At this point a yellow oil was visible and stirring was continued in the ice bath until the oil solidified. The solid was isolated by suction filtration, washed with ice water, dried under reduced pressure to a semi-dry state, the cake was triturated with a spatula to a granular solid, then suspended in fresh ice water, stirred for 15min, and filtered again. The resulting solid was washed with ice water and air dried to give a yellow solid in the form of a powder. Finally, recrystallizing with 180mL of n-hexane to obtain BTPA.
In the embodiment, a visible light-initiated RAFT polymerization method is adopted to synthesize the block polymer, and the block polymer has a soft-hard segment structure, is easy to form a clear hydrophilic-hydrophobic micro-phase separation morphology, and improves the ion transmission efficiency. In addition, the block polymer is functionalized, and a pyrrole group, a trimethylamine group or a piperidine group is introduced into the block polymer, so that the alkali resistance stability of the membrane is improved, and the block anion exchange membrane prepared by the embodiment can have high conductivity and high alkali resistance stability at the same time.
In addition, in the embodiment, the block-type anion exchange membrane is synthesized by adopting a photocatalytic method, the synthesis process can be performed at room temperature without heating or freezing, the operation is simple and convenient, the usage amount of the photocatalyst is small, the ppm-level photocatalyst can efficiently catalyze the polymerization reaction, and the metal residue is small.
This example also provides a block anion exchange membrane having the structural formula:
the block anion exchange membrane has a block structure formed by combining a flexible chain segment and a rigid chain segment, so that the block anion exchange membrane has excellent microphase separation performance, wherein the flexible chain is a polyacrylate segment, and the rigid chain is a polystyrene segment or a fluorine substituted polystyrene segment. In addition, the addition of pyrrole, piperidine and other groups and the addition of fluorine are beneficial to improving the chemical stability of the membrane, including alkali resistance, heat resistance and swelling resistance.
The invention will be further illustrated with reference to the following specific examples. In the following embodiments of the invention, the first monomer is 2-bromoethyl acrylate (Brema), the first chain transfer reagent is 2- (butyltrithiocarbonate) propionic acid (BTPA), the second monomer is styrene, 4-fluorostyrene or pentafluorostyrene, the organic solution comprises dimethyl sulfoxide (DMSO) solution, N, N-Dimethylformamide (DMF), and the photocatalyst is tris (phenylpyridine) iridium complex (Ir (ppy)3)。
Example 1
The embodiment provides a preparation method of a block anion exchange membrane, which comprises the following steps:
1.1 Synthesis of first stage Polymer
Weighing 5mg (0.02mmol) of chain transfer reagent BTPA, adding the BTPA into a 25mL Xinweier reaction tube, vacuumizing, introducing argon, circulating for 3 times to remove the air in the reaction tube, adding BrEMA and Ir (ppy) under argon atmosphere3To obtain a first reaction solution. Wherein the amount of BrEMA added was 0.5mL (4.1mmol), Ir (ppy)3The amount of (2X 10) added was 10ul (1.3g/mL, 2X 10)-5mmol)，DThe amount of MSO added was 0.5 mL.
The first reaction solution was placed under blue LEDs for 30min at room temperature. The power of the blue LEDs is 36Watts, and the maximum incident wavelength lambda max is 456 nm.
After the reaction is finished, adding DMSO into the reaction tube to dilute the first reaction solution, then dropping the first reaction solution into ethanol for precipitation, and repeating the purification for 3 times to obtain pure first-stage polymer poly 2-bromoethyl acrylate (PBrEMA).
1.2 Synthesis of Block Polymer
0.179g of the second chain transfer reagent PBrEMA was weighed, added to a 25mL Xinweier reaction tube, evacuated, and circulated with argon for 3 times to remove the air in the reaction tube, and pentafluorostyrene and Ir (ppy) were added under an argon atmosphere3To obtain a second reaction solution. Wherein, the addition amount of pentafluorostyrene is 124ul (1.0mmol), Ir (ppy)3The amount of (2.5 ul) (1.3g/mL,5ppm, 5X 10)-6mmol), DMSO was added in an amount of 0.5 mL.
The second reaction solution was placed under blue LEDs for 140min at room temperature. The power of the blue LEDs is 36Watts, and the maximum incident wavelength lambda max is 456 nm.
And after the reaction is finished, adding DMSO into the reaction tube to dilute the second reaction solution, dripping the second reaction solution into ethanol to precipitate, and repeatedly purifying for 3 times to obtain the pure block polymer PBrEMA-b-PPFSt.
1.3 functionalization of Block polymers
Dissolving 0.137g of PBrEMA-b-PPFSt in 1.0ml of DMF to form a uniform solution, then adding 80uL of 1-methylpyrrolidine into the solution, placing the reaction solution in an oil bath kettle at 80 ℃ for stirring reaction for 24 hours to obtain a third reaction solution, dropwise adding the third reaction solution into methanol under the stirring condition to precipitate a polymer, and repeatedly purifying the polymer for 3 times to obtain a purified functional polymer PpyEMA-b-PPFSt.
1.4 preparation of Block anion exchange membranes
Dissolving the functional polymer by using chloroform as a solvent to obtain a 10% (w/v) casting solution, pouring the casting solution on a clean and flat glass plate, and drying at room temperature to obtain the block anion exchange membrane.
The IEC of the block anion exchange membrane prepared in this example was 0.87mmol/g by Mohr's titration.
The appearance of the block anion exchange membrane prepared in this example was characterized by microphase separation using a Transmission Electron Microscope (TEM), and the results are shown in fig. 2. As can be clearly seen from fig. 2, the block anion-exchange membrane prepared by the present embodiment has a clear hydrophilic-hydrophobic microphase separation morphology, and the hydrophilic regions are mutually communicated to form a through hydrophilic channel, so as to provide a smooth channel for the transmission of ions, thereby improving the ion transmission efficiency and further improving the conductivity of the anion-exchange membrane. And the hydrophobic region provides mechanical support for the anion exchange membrane, and ensures the mechanical stability of the membrane.
The block anion exchange membrane prepared in this example has such a clear hydrophilic-hydrophobic microphase separation appearance mainly because: the film-forming polymer (functionalized polymer) prepared in this embodiment has a special structure, on one hand, one section of the film-forming polymer contains a hydrophilic pyrrolidinium salt ion functional group, and the other section of pentafluorostyrene is hydrophobic, and on the other hand, the film-forming polymer also has a soft-hard section structure, wherein the first section of the polymer is a flexible chain section, the second section of the polymer is a rigid chain section, the soft-hard section structure is favorable for micro-phase separation to form a through ion channel, and the soft-hard section structure is also favorable for the film to maintain certain mechanical strength.
The block anion exchange membrane prepared in the embodiment has the chlorine type conductivity of 5.94mS/cm at 30 ℃ and is increased to 9.84mS/cm along with the temperature increase to 60 ℃.
Tests prove that the water content of the block anion-exchange membrane prepared in the embodiment is 17.6 wt% at 30 ℃, the linear swelling rate is 1.43%, and the water content and the linear swelling rate are 21.5 wt% and 1.65% respectively when the temperature is raised to 60 ℃.
The block anion exchange membrane prepared in this example was subjected to a strength test as shown in fig. 3, wherein the abscissa strain shown in fig. 3 represents strain in units, and the ordinate strain represents stress in units of MPa. The mechanical strength of the dry film measured by a dynamic mechanical analyzer is 18.3MPa, and the elongation at break is 101.1 percent, which shows that the film has good mechanical properties and can meet the use requirements of fuel cells.
The block anion exchange membrane prepared in this example was subjected to a heat resistance stability test to obtain a thermal decomposition curve of the membrane as shown in FIG. 4, wherein the abscissa Temperature shown in FIG. 4 represents the Temperature in units, and the ordinate weighing retention represents the weight retention of the membrane in units. As shown in FIG. 4, the block anion-exchange membrane prepared in this example starts thermal decomposition at 211 ℃, whereas the operating temperature of a general fuel cell is 60-90 ℃, and the thermal decomposition temperature of the block anion-exchange membrane is much higher than the use temperature of the membrane, so the block anion-exchange membrane prepared in this example has higher heat-resistant stability.
Example 2
This example differs from example 1 in that the first reaction solution was irradiated under blue LEDs at room temperature for 40min, and the second reaction solution was irradiated under blue LEDs at room temperature for 150 min.
Example 3
This example differs from example 1 in that the second reaction solution was irradiated under blue LEDs at room temperature for 120 min.
Example 4
This example differs from example 1 in that the second monomer is styrene.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. A method for preparing a block anion exchange membrane is characterized by comprising the following steps:
taking an acrylate compound containing a functional group precursor as a first monomer, taking 2- (butyl trithiocarbonate) propionic acid as a first chain transfer reagent, and synthesizing a first-stage polymer by adopting a visible light initiated RAFT (reversible addition-fragmentation chain transfer) polymerization method;
synthesizing a block polymer by using the first-stage polymer as a second chain transfer reagent and a styrene compound as a second monomer by adopting a visible light initiated RAFT (reversible addition-fragmentation chain transfer) polymerization method;
adding a functional reagent containing a pyrrole group, a trimethylamine group or a piperidine group into the organic solution of the block polymer, and carrying out quaternization reaction on the first-stage polymer and the pyrrole group, the trimethylamine group or the piperidine group to obtain a functional polymer;
and dissolving the functionalized polymer in a solvent to obtain a membrane casting solution, pouring the membrane casting solution on a substrate, and drying to obtain the block anion exchange membrane.
2. The method of claim 1, wherein the functional group-containing precursor comprises a functionalizable halogen group.
3. The method of claim 2, wherein the first monomer comprises 2-bromoethyl acrylate.
4. The method of claim 2, wherein the functionalizing agent comprises one of 1-methylpyrrolidine, trimethylamine, and N-methylpiperidine.
5. The method of claim 1, wherein the second monomer comprises one of styrene, 4-fluorostyrene, and pentafluorostyrene.
6. The method of claim 1, wherein the molar ratio of the first monomer to the second monomer is 1:2 to 3: 2.
7. The method for preparing the block anion-exchange membrane according to any one of claims 1 to 6, wherein the first-stage polymer is synthesized by the following steps: adding the first chain transfer reagent into a first reaction tube, removing air in the first reaction tube by adopting a vacuumizing and argon circulating method, adding the first monomer and an organic solution of a photocatalyst into the first reaction tube to obtain a first reaction solution, placing the first reaction solution under visible light for irradiation at room temperature, reacting for 20-45min, and after the reaction is finished, diluting, precipitating, filtering and purifying the first reaction solution to obtain a first-stage polymer;
the synthesis process of the block polymer comprises the following steps: adding the first-stage polymer into the second reaction tube, removing air in the second reaction tube by adopting a vacuumizing and argon circulating method, adding the second monomer and the organic solution of the photocatalyst into the second reaction tube to obtain a second reaction solution, placing the second reaction solution under visible light for irradiation at room temperature, reacting for 60-180min, and after the reaction is finished, diluting, precipitating and purifying the second reaction solution to obtain the block polymer.
8. The process for the preparation of a block anion exchange membrane according to any of claims 1 to 6, wherein the functionalized polymer is synthesized by: adding the functional reagent into the organic solution of the block polymer, carrying out quaternization reaction in an oil bath kettle at the temperature of 80-90 ℃ under the stirring condition for 20-24h to obtain a third reaction liquid, dropwise adding the third reaction liquid into methanol under the stirring condition to precipitate a polymer, and purifying the polymer to obtain the functional polymer.
9. A block anion exchange membrane prepared by the method for preparing a block anion exchange membrane according to any of claims 1 to 8.
10. The block anion exchange membrane of claim 9, wherein the structural formula of the block anion exchange membrane is:
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