CN111871222A - Preparation method of quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on pillared [5] arene - Google Patents
Preparation method of quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on pillared [5] arene Download PDFInfo
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Abstract
The invention belongs to the field of preparation of anion exchange membrane materials, and particularly relates to a preparation method of a quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on column [5] arene. Firstly, diamino bisphenol fluorene, bisphenol fluorene and decafluorobiphenyl are used as raw materials, and are condensed and polymerized at low temperature under the catalysis of cesium fluoride to form a fluorine-containing polyfluorene ether compound containing tertiary amino, then the fluorine-containing polyfluorene ether compound and decabromopillared [5] arene react in a polar aprotic solvent, and the obtained reaction liquid is directly cast to form a film, so that a pillared [5] arene modified fluorine-containing polyfluorene ether film is obtained; and then, soaking the obtained pillared [5] arene modified fluorine-containing polyfluorene ether membrane in a trimethylamine aqueous solution for further quaternization to obtain the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on the pillared [5] arene. The anion exchange membrane has the advantages of high ionic conductivity, low vanadium ion permeability, excellent mechanical property and the like, and has wide application prospect in all-vanadium redox flow batteries.
Description
Technical Field
The invention belongs to the field of preparation of anion exchange membrane materials, and particularly relates to a preparation method of a quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on column [5] arene.
Background
The all-vanadium redox flow battery is a type of electrochemical large-scale energy storage equipment which is low in cost, high in energy efficiency and friendly to environment. In recent years, the all-vanadium redox flow battery energy storage system has wide application in the fields of power grid peak regulation, solar energy and wind energy power generation and the like due to the unique advantages of designable power and capacity, high safety and the like.
The anion exchange membrane is a key component of the all-vanadium redox flow battery, and mainly plays a role in selecting charged ion ions in electrolyte to form a battery loop and isolating the two electrolytes in the all-vanadium redox flow battery. At present, the anion exchange membrane for the all-vanadium redox flow battery mainly has the problems of poor ion conduction performance and the like, and the development of commercialization of the anion exchange membrane is hindered. The ion conductivity of the membrane can be improved by increasing the ion exchange capacity of the anion exchange membrane, but the membrane is excessively swollen by water absorption, so that the mechanical property and chemical stability of the membrane are reduced. Under the condition of keeping similar ion exchange capacity, a direct and effective method for improving the ion conduction performance is to ensure that ion exchange groups are densely distributed on a polymer skeleton through molecular design, so that hydrophilic ion group parts can be mutually aggregated in the film forming process to form an ion transmission channel to promote the ion conduction.
The columnar arene is a novel macrocyclic main organic compound with a columnar molecular structure, and the macrocyclic main organic compound consists of benzene ring units connected by methylene bridges at para positions. Due to the rigid columnar electron-rich cavity structure and the unique chemical properties of the host and the guest, the columnar aromatic hydrocarbon has been widely noticed and researched since the self-report, and has strong application potential in the fields of functional supermolecules, advanced porous materials, chemical sensors and the like. In addition, the phenolic hydroxyl on the main aromatic ring of the columnar aromatic hydrocarbon has the characteristic of easy functionalization, and the method can be used for preparing various columnar aromatic hydrocarbon derivatives and is applied to different material research fields. The preparation process of the column [5] arene and the column [6] arene in the column arene family is simple, the raw materials are low in price, and the method is an ideal component for constructing a functional material. However, reports on the anion exchange membrane material of the all-vanadium flow battery with the quaternary ammonium salt functionalized column [5] arene used as the functionalized structure are less.
Therefore, the column [5] arene is introduced into the anion exchange membrane, and the anion exchange membrane with excellent ion conduction performance and chemical stability is developed, so that the method has important significance for the development of the all-vanadium redox flow battery.
Disclosure of Invention
The invention aims to provide a preparation method of a quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on column [5] arene. The prepared quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on the column [5] arene has the advantages of simple process, high ionic conductivity, high chemical stability and the like, and has important application prospect in the field of ion exchange membranes.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on pillared [5] arene comprises the steps of reacting fluorine-containing polyfluorene ether compound containing tertiary amino with decabromopillared [5] arene in a polar aprotic solvent, directly casting the obtained reaction liquid into a membrane, and then soaking the membrane in trimethylamine aqueous solution for further quaternization to obtain the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on pillared [5] arene; the method specifically comprises the following steps:
(1) adding diamino bisphenol fluorene, bisphenol fluorene and decafluorobiphenyl into a polar aprotic solvent, stirring under the protection of an inert atmosphere to completely dissolve solids, then sequentially adding calcium hydride and cesium fluoride, and carrying out a polymerization reaction at 0-40 ℃ for 5-50 hours; then, pouring the product into deionized water with the volume 10-100 times of that of the polar aprotic solvent to separate out a precipitate, filtering and collecting the precipitate, and drying the precipitate in a vacuum oven at the temperature of 40-60 ℃ for 10-40 hours to obtain a fluorine-containing polyfluorene ether compound containing tertiary amino;
the fluorine-containing polyfluorene ether compound containing tertiary amine groups has the following chemical structure:
wherein m is 1 to 400 and n is 10 to 400.
(2) Dissolving the fluorine-containing polyfluorene ether compound containing tertiary amino groups obtained in the step (1) in a polar aprotic solvent to prepare a 1-5 wt.% solution A; dissolving decabromocolumn [5] arene in a polar aprotic solvent to prepare a solution B of 5-10 wt.%; dropwise adding the solution A into the solution B at the speed of 1-5 mL/min at the temperature of 0-40 ℃ under the protection of inert atmosphere, and then continuously stirring for 10-20 hours at the temperature of 0-40 ℃; then, casting the reaction liquid on a horizontally placed glass plate, drying for 10-50 hours in a common drying oven at 40-100 ℃, and then drying for 10-50 hours in a vacuum drying oven at 60-150 ℃ to obtain a column [5] arene modified fluorine-containing polyfluorene ether film;
the chemical structure of the decabromocolumn [5] arene is as follows:
(3) and (3) soaking the column [5] arene modified fluorine-containing polyfluorene ether membrane obtained in the step (2) in 5-10 wt% of trimethylamine aqueous solution for 20-50 hours at room temperature, and then soaking in deionized water for 20-50 hours to obtain the column [5] arene-based quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane.
For the convenience of understanding, the chemical structure of the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on the column [5] arene is shown as follows:
in the formula
Is a polyfluorene ether segment, -R is
In the step (1), the molar ratio of diamino bisphenol fluorene, decafluorobiphenyl, calcium hydride and cesium fluoride is x: (1-x): 1: (0.01-1): (3-6), wherein 0< x < 1; the ratio of the volume of the polar aprotic solvent to the molar amount of decafluorobiphenyl is 1 to 5 mL: 1 mmol.
The molar weight of the decabromopillared [5] arene used in the step (2) is equal to the molar weight of the tertiary amine group contained in the fluorine-containing polyfluorene ether compound containing the tertiary amine group.
The ratio of the mass of the aromatic hydrocarbon modified fluorine-containing polyfluorene ether film in the column [5] in the step (3) to the volume of the trimethylamine aqueous solution is 1g: 500-5000 mL; the ratio of the mass of the column [5] arene modified fluorine-containing polyfluorene ether film to the volume of deionized water is 1g: 500-5000 mL.
In order to better implement the present invention, the polar aprotic solvent in the above step is any one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, and 1, 3-dimethyl-2-imidazolidinone.
The thickness of the obtained quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on the column [5] arene is 40-80 microns.
The quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on the column [5] arene can be used as a diaphragm material of an all-vanadium flow battery.
Compared with the prior art, the invention has the following effects:
(1) the raw materials adopted by the invention are common chemical raw materials, are low in price and are easy to obtain;
(2) the quaternary ammonium salt group is introduced through the reaction of the tertiary amine and the alkyl bromide, the reaction condition is mild, and the ion exchange capacity of the membrane can be controlled by adjusting the content of the tertiary amine in the polymer;
(3) the anion exchange membrane adopts a fluorine-containing polyarylether framework, and has excellent mechanical property and chemical stability;
(4) the anion exchange membrane prepared by the invention contains a column [5] arene structure, each three-dimensional annular column [5] arene unit is connected with ten quaternary ammonium salt chain segments, the quaternary ammonium salt ions are highly dense, an ion channel in a three-dimensional space is easy to form in the membrane forming process, and the obtained anion exchange membrane has excellent ion conductivity.
Drawings
FIG. 1 shows the NMR spectrum of PFETA-5, a fluorine-containing polyarylether compound containing tertiary amine groups prepared in example 1 of the present invention.
FIG. 2 shows an IR spectrum of a fluorine-containing polyarylether compound PFETA-5 containing tertiary amine groups prepared in example 1 of the present invention.
FIG. 3 shows the NMR spectrum of a column [5] arene-modified fluorine-containing polyfluoroether membrane BrP-PFE-5 prepared in example 5 of the present invention.
FIG. 4 is an IR spectrum of a column [5] arene-modified fluorine-containing polyfluoroether film BrP-PFE-5 prepared in example 5 of the present invention.
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of QAP-PFE-5, a quaternary ammonium salt functionalized fluorine-containing polyfluoroether anion exchange membrane based on column [5] arene prepared in the embodiment 7 of the invention.
FIG. 6 is an infrared spectrum of QAP-PFE-5, a quaternary ammonium salt functionalized fluorine-containing polyfluoroether anion exchange membrane based on column [5] arene prepared in example 7 of the present invention.
FIG. 7 shows 120mAcm of all-vanadium redox flow battery assembled by examples 7 and 8 of the invention and comparative examples 1 and 2-2Graph of cycle number-capacity retention rate.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
The diaminobisphenol fluorene used was synthesized as described in the reference J Polym Sci Pol Chem,2016,54: 935-944, and has the following chemical formula:
the decabromous column [5]]The aromatic hydrocarbon reference (J Am Chem Soc,2016,138:754-757) has a chemical structural formula:
EXAMPLE 1 preparation of fluorine-containing polyfluorene ether Compound PFETA-5 containing Tertiary amino groups
0.3716g (0.20mmol) of diaminobisphenol fluorene, 1.3316g (3.80mmol) of bisphenol fluorene, 1.3365 g (4.00mmol) of decafluorobiphenyl and 10mL of N-methylpyrrolidone were placed in a 25mL three-necked round-bottomed flask. The solid was completely dissolved by magnetic stirring under argon, followed by addition of 0.17g (4mmol) of calcium hydride and 2.43g (16mmol) of cesium fluoride in that order and stirring at room temperature for 24 hours. After the reaction, the mixture was poured into 500mL of deionized water to precipitate a strip-like precipitate. The precipitate was collected by filtration and dried in a vacuum oven at 60 ℃ for 24 hours to obtain a fluorine-containing polyfluorene ether compound PFETA-5 containing tertiary amino groups with a yield of 96%. The data of the nuclear magnetic resonance hydrogen spectrum of the compound are as follows:1h NMR (600MHz, Chloroform-d)7.78(s,10H), 7.39(s,20H),7.30(s,4H),7.21(s,20H),6.93(s,20H),3.62(s,1H),2.20(s, 4H). The infrared spectrum data are as follows: FT-IR (cm)-1)υ3064，3041，2925，1693，1646，1601，1486，1207，1170， 1072，982，818，746，729。
Example 2 preparation of fluorine-containing polyfluorene ether Compound PFETA-10 having Tertiary amino groups
The same procedures as in example 1 were repeated except for replacing the charged amount of diaminobisphenol fluorene in example 1 with 0.1858g (0.40mmol) and replacing the charged amount of bisphenol fluorene with 1.2615g (3.60mmol), to obtain a fluorine-containing polyfluorene ether compound PFETA-10 containing tertiary amino groups in yield: 98 percent.
Example 3 preparation of fluorine-containing polyfluorene ether Compound PFETA-40 having Tertiary amine group
The same procedures as in example 1 were repeated except for replacing the charged amount of diaminobisphenol fluorene in example 1 with 0.7432g (1.60mmol) and replacing the charged amount of bisphenol fluorene with 0.8410g (2.40mmol), to obtain a fluorine-containing polyfluorene ether compound PFETA-40 containing tertiary amino groups at a yield: 98 percent.
Example 4 preparation of fluorine-containing polyfluorene ether Compound PFETA-70 having Tertiary amine group
The same procedures as in example 1 were repeated except for replacing the charged amount of diaminobisphenol fluorene in example 1 with 1.3006g (2.80mmol) and 0.4205g (1.20mmol) of bisphenol fluorene, to obtain a fluorine-containing polyfluorene ether compound PFETA-70 containing tertiary amino groups at a yield: 96 percent.
Example 5 preparation of column [5] aromatic-modified fluorine-containing polyfluoroether film BrP-PFE-5
1.00g (1.54mmol) of the fluorine-containing polyfluorene ether compound PFETA-5 containing a tertiary amino group obtained in example 1 was dissolved in 20mL of N, N-dimethylacetamide to prepare a 5 wt.% solution A; then 0.55g (0.30mmol) of decabromous column [5]]Aromatic hydrocarbons were dissolved in 10ml of N, N-dimethylacetamide to make 9.1 wt.% solution B; under the protection of argon atmosphere, the solution A is dropwise added into the solution B at the speed of 1mL/min at 25 ℃, and then the reaction is continuously stirred at 25 ℃ for 10 hours. Then, the reaction solution was cast on a flat glass plate placed horizontally, dried in a common oven at 80 ℃ for 12 hours, then dried in a vacuum oven at 120 ℃ for 24 hours, cooled and then immersed in deionized water to peel off the film from the glass plate, and the column [5] was obtained]The aromatic hydrocarbon modified fluorine-containing polyfluorene ether film BrP-PFE-5 has a yield of 94%. The data of the nuclear magnetic resonance hydrogen spectrum are:1h NMR (600MHz, Chloroform-d)7.78 (d, J ═ 7.5Hz,3H),7.35(m,6H),7.25(m,5H),6.91(d, J ═ 8.3Hz,5H),6.78(s, 1H),4.18(m,4H),3.79(s,1H),3.56(t,1H),2.30(m, 1H). The infrared spectrum data are as follows: FT-IR (cm)-1)υ3365，3066，3037，2935，2875，2402，2360，1961，1646，1602， 1489，1288，1207，1170，1072，979，821，750，732，615，569。
Example 6 preparation of column [5] aromatic-modified fluorine-containing polyfluoroether film BrP-PFE-10
The procedure of example 5 was repeated except for replacing 1.00g (1.54mmol) of the fluorine-containing polyfluorene ether compound containing tertiary amino groups PFETA-5 in example 5 with 0.51g (0.77mmol) of the fluorine-containing polyfluorene ether compound containing tertiary amino groups PFETA-10 obtained in example 2 to obtain a column [5] arene-modified fluorine-containing polyfluorene ether film BrP-PFE-10 in a yield of 92%.
EXAMPLE 7 preparation of Quaternary ammonium functionalized fluorinated polyfluoroether anion exchange Membrane QAP-PFE-5 based on pillared [5] arenes
1.00g (1.20mmol) of the column [5] obtained in example 5 was introduced]Soaking the aromatic hydrocarbon modified fluorine-containing polyfluorene ether film BrP-PFE-5 in 500mL 10 wt% trimethylamine aqueous solution at room temperature for 24 hours; then soaking the column in 1000mL of deionized water for 24 hours at room temperature to obtain the column [5]]The quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane QAP-PFE-5 of the aromatic hydrocarbon has the yield of 95 percent. The data of the nuclear magnetic resonance hydrogen spectrum of the compound are as follows:1h NMR (600MHz, Chloroform-d)7.93(s,1H),7.42(s,2H),7.31(s,1H),7.12(s,5H), 6.81(s,1H),4.02(m,2H),3.76(m,3H),3.31(s,1H),2.51(s,2H),2.30(s,2H),2.19 (t,1H),1.91(p 1H). The infrared spectrum data are as follows: FT-IR (cm)-1)υ3058，2037，2927，2858，1693， 1649，1602，1487，1205，1072，981，819，746，728。
Example 8 preparation of Quaternary ammonium salt functionalized fluorinated polyfluoroether anion exchange membrane QAP-PFE-10 based on column [5] arene
The procedure of example 7 was repeated except for replacing 1.00g (1.20mmol) of the column [5] arene-modified fluorine-containing polyfluoroether membrane BrP-PFE-5 of example 7 with 0.68g (0.6mmol) of the column [5] arene-modified fluorine-containing polyfluoroether membrane BrP-PFE-10 obtained in example 6 to obtain a column [5] arene-based quaternary ammonium salt functionalized fluorine-containing polyfluoroether anion exchange membrane QAP-PFE-10 with a yield of 94%.
Comparative example 1 preparation of Single Quaternary ammonium salt type fluorine-containing polyfluorene ether anion exchange membrane QA-PFE-40
1.00g (1.45mmol) of the fluorine-containing polyfluorene ether compound PFETA-40 containing a tertiary amino group obtained in example 3 was dissolved in 20mL of N, N-dimethylacetamide to prepare a 5 wt.% solution. And then casting the solution on a flat glass which is horizontally placed, drying the flat glass in a common oven at the temperature of 80 ℃ for 12 hours, drying the flat glass in a vacuum drying oven at the temperature of 120 ℃ for 24 hours, and peeling the film from the glass plate in deionized water after cooling to obtain the PFETA-40 compound film. Immersing the PFETA-40 compound film into 5 wt% methyl iodide aqueous solution with the volume of 500mL, and soaking for 24 hours at the temperature of 20 ℃; then soaking the mixture in 1000mL of NaBr aqueous solution with the concentration of 0.5mol/L for 24 hours at the temperature of 20 ℃, and then soaking the mixture in 1000mL of deionized water for 24 hours to obtain the single quaternary ammonium salt type fluorine-containing polyfluorene ether compound QA-PFE-40 with the yield of 95%. The chemical structural formula is as follows:
Comparative example 2 preparation of Single Quaternary ammonium salt type fluorine-containing polyfluorene ether anion exchange Membrane QA-PFE-70
The same procedure as in comparative example 1 was repeated except for replacing 1.00g (1.45mmol) of the fluorine-containing polyfluorene ether compound PFETA-40 containing tertiary amino groups in comparative example 1 with 0.60g (0.83mmol) of the fluorine-containing polyfluorene ether compound PFETA-70 containing tertiary amino groups obtained in example 4 to obtain a single quaternary ammonium salt type fluorine-containing polyfluorene ether anion exchange membrane QA-PFE-70, which was obtained at a yield of 95%.
The ion exchange capacity is measured by an acid-base titration method, the chloride ion conductivity of the membrane is measured by an alternating current impedance method, and the mechanical property of the membrane is evaluated by a tensile experiment. The water absorption was calculated by measuring the change in weight measurements of dry and wet samples. Detection of VO through the membrane by UV spectroscopy2+The vanadium ion permeability of the film was evaluated by the change in ion concentration. Prepared based on column [5]]The performance ratio of the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane of the aromatic hydrocarbon and the single-quaternary ammonium salt type fluorine-containing polyfluorene ether reference membrane is shown in table 1.
TABLE 1 comparison of Performance of Quaternary ammonium salt functionalized fluorinated polyfluorene ether anion exchange membranes based on column [5] arene and monoquaternary ammonium salt type fluorinated polyfluorene ether reference membranes
The test results in table 1 show that the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on the column [5] arene has higher ion conductivity and lower vanadium ion transmittance than a single-quaternary ammonium salt fluorine-containing polyfluorene ether anion exchange membrane under similar ion exchange capacity, and the introduction of the column [5] arene promotes the ion conductivity of the anion exchange membrane. In addition, under the condition of higher ion exchange capacity, the mechanical property of the single-quaternary ammonium salt type fluorine-containing polyfluorene ether-based anion exchange membrane is obviously reduced due to overhigh water absorption rate, and the water absorption rate of the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether-based anion exchange membrane based on the column [5] arene is increased to a smaller extent along with the increase of the ion exchange capacity, so that the good mechanical property is still maintained.
The prepared fluorine-containing polyfluorene ether anion exchange membrane is filled into an all-vanadium redox flow battery at the concentration of 80mA cm-2Cell efficiency was tested at current density of (a). At the same time, the current is passed through the battery at 120mA cm-2The cycle stability of the film was evaluated on the discharge capacity retention rate after 50 cycles at the current density of (1). Preparation based on column [5]]The ratio of all-vanadium performance of the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane of the aromatic hydrocarbon to that of the single-quaternary ammonium salt fluorine-containing polyfluorene ether reference membrane is shown in table 2.
TABLE 2 comparison of the performance of quaternary ammonium salt functionalized fluorinated polyfluorene ether anion exchange membrane based on column [5] arene and a monoquaternary ammonium salt type fluorinated polyfluorene ether reference membrane
The test results in table 2 show that the all-vanadium redox flow battery assembled by the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on the column [5] arene has higher coulombic efficiency, voltage efficiency and energy efficiency than the battery assembled by the single-quaternary ammonium salt type fluorine-containing polyfluorene ether reference membrane under similar ion exchange capacity. This result can be attributed to the column [5] arene-based quaternary ammonium salt functionalized polyfluoroether-containing anion exchange membranes having higher ionic conductivity and lower vanadium ion permeability than the reference membranes. Meanwhile, the all-vanadium redox flow battery assembled by the quaternary ammonium salt functionalized fluorine-containing polyfluoroether anion exchange membrane based on the column [5] arene has higher cycle stability and still has a capacity retention rate of more than 88% after 50 cycles (shown in figure 7). Therefore, the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on the column [5] arene has great application potential in the all-vanadium flow battery.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. A preparation method of a quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on column [5] arene is characterized in that diaminobisphenol fluorene, bisphenol fluorene and decafluorobiphenyl are used as raw materials, a fluorine-containing polyfluorene ether compound containing tertiary amino is polymerized in a low-temperature condensation mode under the catalysis of cesium fluoride, then the fluorine-containing polyfluorene ether compound and decabromocolumn [5] arene react in a polar aprotic solvent, and the obtained reaction liquid is directly cast into a membrane to obtain a column [5] arene modified fluorine-containing polyfluorene ether membrane; and then, soaking the obtained column [5] arene modified fluorine-containing polyfluorene ether membrane in trimethylamine aqueous solution for further quaternization, and finally obtaining the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on the column [5] arene.
2. The preparation method of the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on the column [5] arene, according to claim 1, is characterized by comprising the following steps:
(1) adding diamino bisphenol fluorene, bisphenol fluorene and decafluorobiphenyl into a polar aprotic solvent, stirring under the protection of an inert atmosphere to completely dissolve solids, then sequentially adding calcium hydride and cesium fluoride, and stirring for reaction; then, pouring the product into deionized water with the volume 10-100 times of that of the polar aprotic solvent to separate out a precipitate, filtering, collecting the precipitate, and performing vacuum drying to obtain a fluorine-containing polyfluorene ether compound containing tertiary amino;
the fluorine-containing polyfluorene ether compound containing tertiary amine groups has the following chemical structure:
wherein m is 1 to 400 and n is 10 to 400.
(2) Dissolving the fluorine-containing polyfluorene ether compound containing tertiary amino groups obtained in the step (1) in a polar aprotic solvent to prepare a 1-5 wt.% solution A; dissolving decabromocolumn [5] arene in a polar aprotic solvent to prepare a solution B of 5-10 wt.%; dropwise adding the solution A into the solution B under the protection of inert atmosphere, and then continuously stirring for 10-20 hours at 0-40 ℃; then, casting the reaction liquid on a horizontally placed glass plate, and drying in a common oven and a vacuum oven in sequence to obtain a column [5] arene modified fluorine-containing polyfluorene ether film;
the chemical structure of the decabromocolumn [5] arene is as follows:
(3) and (3) soaking the column [5] arene modified fluorine-containing polyfluorene ether membrane obtained in the step (2) in 5-10 wt% of trimethylamine aqueous solution for 20-50 hours at room temperature, and then soaking in deionized water for 20-50 hours to obtain the column [5] arene-based quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane.
3. The preparation method of the quaternary ammonium salt functionalized fluorine-containing polyfluoroether anion-exchange membrane based on the pillared [5] arene, which is characterized in that the molar ratio of diamino bisphenol fluorene, decafluorobiphenyl, calcium hydride and cesium fluoride in the step (1) is x: (1-x): 1: (0.01-1): (3-6), wherein 0< x < 1; the ratio of the volume of the polar aprotic solvent to the molar amount of decafluorobiphenyl is 1 to 5 mL: 1 mmol.
4. The preparation method of the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion-exchange membrane based on the column [5] arene, according to claim 2, is characterized in that the stirring reaction in the step (1) is specifically polymerization at 0-40 ℃, and the reaction lasts for 5-50 hours; the vacuum drying is specifically drying in a vacuum oven at 40-60 ℃ for 10-40 hours.
5. The method for preparing the column [5] arene-based quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane according to claim 2, wherein the molar amount of the decabromocolumn [5] arene used in the step (2) is equal to the molar amount of the tertiary amine group contained in the fluorine-containing polyfluorene ether compound containing the tertiary amine group.
6. The preparation method of the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on the column [5] arene, according to claim 2, wherein the dripping step in the step (2) is specifically: dripping at 0-40 ℃ at the speed of 1-5 mL/min.
7. The preparation method of the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on the column [5] arene, according to claim 2, wherein the drying step in the step (2) is specifically: drying the mixture in a common oven at 40-100 ℃ for 10-50 hours, and then drying the mixture in a vacuum drying oven at 60-150 ℃ for 10-50 hours.
8. The preparation method of the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion-exchange membrane based on the pillared [5] arene according to claim 2, wherein the ratio of the mass of the pillared [5] arene modified fluorine-containing polyfluorene ether membrane in the step (3) to the volume of the trimethylamine aqueous solution is 1g: 500-5000 mL; the ratio of the mass of the column [5] arene modified fluorine-containing polyfluorene ether film to the volume of deionized water is 1g: 500-5000 mL.
9. Column [5] according to claim 2]The preparation method of the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane of the aromatic hydrocarbon is characterized in that the polar aprotic solvent isN,N-dimethylacetamide,N,N-dimethylformamide,NAny one of methyl pyrrolidone, dimethyl sulfoxide and 1, 3-dimethyl-2-imidazolidinone.
10. The application of the quaternary ammonium salt functionalized fluorine-containing polyfluorene ether anion exchange membrane based on the column [5] arene prepared by the method of any one of claims 1 to 9 to a diaphragm of an all-vanadium flow battery.
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