CN115558169A - Preparation method of bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity - Google Patents

Preparation method of bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity Download PDF

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CN115558169A
CN115558169A CN202211177595.9A CN202211177595A CN115558169A CN 115558169 A CN115558169 A CN 115558169A CN 202211177595 A CN202211177595 A CN 202211177595A CN 115558169 A CN115558169 A CN 115558169A
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microsphere
chitosan
proton conductivity
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杨新林
刘芙瑶
孙遵明
杨景子俊
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Nankai University
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Abstract

The invention discloses a preparation method of a bell-type amphoteric ion microsphere chitosan hybrid membrane with high proton conductivity. The method comprises the following steps: tetraethyl silicate is used as a raw material to synthesize silicon spheres, styrene and divinylbenzene are coated on the outer layer of the silicon spheres through a distillation precipitation polymerization method, the inner core is selectively etched by hydrofluoric acid to obtain small bell type microspheres, amino groups and sulfonic groups are respectively modified on the inner core and the shell layer of the small bell type microspheres to obtain double small bell type microspheres, and the double ionic microsphere chitosan hybrid membrane is loaded into chitosan to prepare the small bell type double ionic microsphere chitosan hybrid membrane. The bell-type amphoteric ion microsphere chitosan hybrid membrane for the proton exchange membrane has high proton conductivity and oxidation stability. Has important significance for the development of the field of proton exchange membrane materials.

Description

Preparation method of bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity
Technical Field
The invention belongs to the technical field of proton exchange membrane preparation, and particularly relates to a bell-type zwitter-ion microsphere chitosan hybrid membrane with high proton conductivity and a preparation method thereof.
Background
Human convenience depends on advanced science and technology, but it also causes the decay of fossil energy. Therefore, the development of renewable energy is a main solution. The proton exchange membrane fuel cell is the fifth generation fuel cell which is under development and is characterized in that a solid proton exchange membrane is used as an electrolyte. The function of the proton exchange membrane is to separate the fuel and oxidant, to support the catalyst, and to conduct the protons. Among them, having high proton conductivity is the most important requirement for proton exchange membrane. The high proton conductivity can enable the battery to obtain higher current density and power density during operation, so that the performance of the battery is better. On the other hand, strong oxidizing radicals are generated during the operation of the battery, and attack the main polymer chain to cause membrane degradation, which causes great limitation to the application of the proton exchange membrane. The chitosan is a deacetylated product of chitin, is rich in environment, belongs to natural macromolecules, and has good film forming property. However, due to the lack of mobile hydrogen ions in the membrane, the proton conductivity is low, and the oxidation stability of the chitosan membrane is poor, and the chitosan membrane needs to be modified to improve the performance of the chitosan membrane. Currently common modification methods include sulfonation, phosphorylation, chemical crosslinking, and the like. However, the proton conductivity of the modified chitosan-based membrane is improved to a limited extent, and the oxidation stability is poor, so that the requirement of the proton exchange membrane material is difficult to meet, and therefore, the development of a preparation method of the chitosan-based proton exchange membrane material with high proton conductivity and oxidation stability is urgently needed.
Disclosure of Invention
The invention aims to provide a preparation method of a bell-type zwitter-ion microsphere chitosan hybrid membrane with high proton conductivity, which aims to solve the problems of low proton conductivity and poor oxidation stability of a chitosan-based proton exchange membrane material.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the preparation method of the bell-type zwitter-ion microsphere chitosan hybrid membrane with high proton conductivity comprises the following steps:
s1, adding ethanol, water and ammonium hydroxide into a reactor according to a certain proportion, mechanically stirring, adding tetraethyl silicate, mechanically stirring, adding 3- (methacryloyl) propyl trimethoxy silane, mechanically stirring, centrifuging to obtain a reactant, washing with absolute ethanol, and vacuum drying to obtain a product a.
And S2, dispersing the product a prepared in the step S1 into acetonitrile, adding divinylbenzene, styrene and 2, 2-azobisisobutyronitrile, reacting under a reflux condition, centrifuging out a reactant, washing with absolute ethyl alcohol, and drying in vacuum to obtain a product b.
And S3, dispersing the product b prepared in the step S2 into absolute ethyl alcohol, adding a hydrofluoric acid solution, centrifuging out a reactant after reaction, washing with absolute ethyl alcohol, and drying in vacuum to obtain a product c.
And S4, dispersing the product c prepared in the step S3 into toluene, adding 3-aminopropyl trimethoxy silane, reacting under a reflux condition, centrifuging to obtain a reactant, washing with absolute ethyl alcohol, and drying in vacuum to obtain a product d.
S5, dispersing the product d prepared in the step S4 into trichloromethane, dropwise adding chlorosulfonic acid, centrifuging the reaction product after reaction, washing the reaction product with absolute ethyl alcohol, and drying the reaction product in vacuum to obtain a product e: bell type zwitterionic microspheres.
S6, mixing the product e prepared in the step S5: and dispersing the bell-type zwitterionic microspheres into acetic acid to obtain a solution f.
S7, dissolving chitosan in acetic acid to obtain a solution g.
S8, mixing and stirring the solution f prepared in the step S6 and the solution g prepared in the step S7 to obtain a mixed solution h.
S9, casting the mixed solution h prepared in the step S8 on a glass plate, and drying to obtain a product i.
And S10, soaking the product i prepared in the step S9 in sulfuric acid, washing with deionized water until a washing solution is neutral, and performing vacuum drying to obtain the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity.
Preferably, the ratio of the used raw materials and the conditions in step S1 are as follows: 100-120mL of ethanol, 10-13mL of water and 2-2.5mL of ammonium hydroxide, wherein the mechanical stirring speed is 350-450r/min, and the time is 20 min-1 h; adding 5-8mL tetraethyl silicate in proportion, and mechanically stirring at the speed of 350-450r/min for 2-12h; adding 1-3mL of 3- (methacryloyl) propyl trimethoxy silane according to the proportion, wherein the mechanical stirring speed is 350-450r/min, and the time is 12h; the reaction temperature is room temperature, the centrifugation condition is 8000r/min, the time is 8min, and then the vacuum drying is carried out, the temperature is 50-60 ℃, and the drying time is 8-24h.
Preferably, each gram of the product a in the step S2 corresponds to 200-250mL of acetonitrile solvent, 1.0-2.0mL of divinylbenzene, 1.0-2.0mL of styrene and 0.05-1.0g of 2, 2-azobisisobutyronitrile, the reaction time is 3.5h under the reflux condition, the centrifugation condition is 6000r/min and the time is 8min, and the final centrifugation and drying conditions are the same as the above.
Preferably, each gram of the product b in the step S3 corresponds to 50-80mL of solvent ethanol, 50-80mL of hydrofluoric acid solution with the mass concentration of 1%, the reaction time is 80min, the centrifugation condition is 8000 rpm, the reaction time is 8min, and the final centrifugation and drying conditions are the same as above.
Preferably, each gram of the product c in the step S4 corresponds to 200-250mL of toluene solvent, 2-3mL of 3-aminopropyl trimethoxy silane solvent, the reaction time is 12h under the reflux condition, the centrifugation condition is 8000r/min, the reaction time is 8min, and the final centrifugation and drying conditions are the same as the above.
Preferably, in the step S5, each gram of the product d corresponds to 80-100mL of chloroform as a solvent, 0.8-1.0mL of chlorosulfonic acid is dropwise added after ice bath is carried out to the temperature of 0 ℃, the reaction time is 2h after the dropwise addition of chlorosulfonic acid is finished, the temperature condition is 30-60 ℃, the centrifugation condition is 8000r/min, and the time is 8min. The final centrifugation and drying conditions were as above.
Preferably, in the step S6, each gram of the product e corresponds to 240-260mL of acetic acid, the mass concentration is 2%, the ultrasonic treatment is carried out for 30min, and the temperature is room temperature. Each gram of product e in step S6 corresponds to 10-12 grams of chitosan in step S7.
Preferably, in the step S7, 25-30mL of acetic acid with the mass concentration of 20% is corresponding to each gram of chitosan, the reaction temperature is 80 ℃, and the reaction time is 2h.
Preferably, the stirring temperature in step S8 is 80 ℃ and the reaction time is 2h.
Preferably, the drying conditions in step S9 are room temperature and drying is carried out until the quality of the product is unchanged.
Preferably, the sulfuric acid concentration in step S10 is 2M and the soaking time is 24h. The drying temperature is 25 ℃, and the bell-type zwitter-ion microsphere chitosan hybrid membrane with high proton conductivity of the product is obtained after the quality is unchanged.
The invention has the advantages and beneficial effects that:
the process of the invention adopts reflux precipitation polymerization, has simple operation process, complete appearance of the synthesized product and good dispersibility.
The bell-type amphoteric ion microspheres prepared by the process have a cavity structure capable of storing water, and the water retention of the membrane is improved by the hybrid membrane loaded in chitosan.
The bell-type amphoteric ion microspheres prepared by the process have acid and alkali functional groups at the same time, and hybrid membranes prepared by loading the microspheres in chitosan have high proton conductivity.
The bell-type zwitterionic microsphere chitosan hybrid membrane prepared by the process has high oxidation stability.
Detailed Description
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
In the embodiment of the invention, the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity comprises the following raw materials: tetraethyl silicate, 3- (methacryloyl) propyltrimethoxysilane, 2-azobisisobutyronitrile. Divinylbenzene (80%), 3-aminopropyltrimethoxysilane (97%), hydrofluoric acid (1%), ethanol (99%), acetonitrile (99%), chlorosulfonic acid (99%), ammonium hydroxide (25 wt%), toluene (99%), chloroform, chitosan (degree of deacetylation 91%), sulfuric acid (98%), deionized water.
Example 1
A preparation method of a bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity comprises the following steps:
s1, adding 100mL of ethanol, 11mL of water and 2.0mL of ammonium hydroxide into a reactor, mechanically stirring at 400r/min for 1h, then adding 6mL of tetraethyl silicate, mechanically stirring at 400r/min for 2h, then adding 1.5mL of 3- (methacryloyl) propyl trimethoxysilane, mechanically stirring at 400r/min for 12h, centrifuging to obtain a reactant, washing with absolute ethanol for 3 times, and vacuum-drying at 60 ℃ for 8h to obtain a product a.
S2, dispersing 1 g of the product a prepared in the step S1 into 250mL of acetonitrile, adding 2mL of divinylbenzene, 2mL of styrene and 0.08g of 2, 2-azobisisobutyronitrile, reacting for 3.5h under the reflux condition, then 6000r/min, centrifuging for 8min, centrifuging out the reactant, washing for 3 times by using absolute ethyl alcohol, and drying for 8h under vacuum at 60 ℃ to obtain a product b.
And S3, dispersing 1 g of the product b prepared in the step S2 into 70mL of absolute ethyl alcohol, adding 70mL of hydrofluoric acid solution with the mass concentration of 1% to react for 80min, then centrifuging for 8min at 8000r/min to obtain a reactant, washing for 5 times by using absolute ethyl alcohol, and carrying out vacuum drying for 8h at 60 ℃ to obtain a product c.
S4, dispersing 1 g of the product c prepared in the step S3 into 235mL of toluene, adding 2.5mL of 3-aminopropyltrimethoxysilane, reacting for 12h under the reflux condition, then centrifuging for 8min at 8000r/min, centrifuging out the reactant, washing for 3 times by using absolute ethyl alcohol, and drying for 8h in vacuum at 60 ℃ to obtain a product d.
S5, dispersing 1 g of the product d prepared in the step S4 into 82mL of chloroform, carrying out ice bath until the temperature is 0 ℃, and then dropwise adding 0.82mL of chlorosulfonic acid. Then the temperature is increased to 30 ℃ for reaction for 2h. Centrifuging for 8min at 8000r/min after reaction, centrifuging to obtain a reactant, washing for 3 times by using absolute ethyl alcohol, and drying for 8h in vacuum at 60 ℃ to obtain a product e: bell type zwitterionic microspheres.
S6, 1 g of the product e prepared in the step S5: and dispersing the bell-type zwitter-ion microspheres into 250mL of acetic acid with the mass concentration of 2%, and performing ultrasonic treatment for 30min at room temperature to obtain a solution f.
S7, dissolving 10 g of chitosan in 300mL of acetic acid with the mass concentration of 20%, and reacting at 80 ℃ until the chitosan is completely dissolved to obtain a solution g.
And S8, mixing and stirring the solution f prepared in the step S6 and the solution g prepared in the step S7 at 80 ℃ for 2h to obtain a mixed solution h.
And S9, casting the mixed solution h prepared in the step S8 on a glass plate, and drying at room temperature to obtain a product i.
S10, putting the product i prepared in the step S9 into sulfuric acid with the concentration of 2M for soaking for 24h, washing with deionized water until a washing solution is neutral, and performing vacuum drying at room temperature to obtain the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity, wherein the proton conductivity and the oxidation stability are respectively shown in tables 1 and 2.
Example 2
S1, adding 100mL of ethanol, 11mL of water and 2.0mL of ammonium hydroxide into a reactor, mechanically stirring for 1h at 400r/min, then adding 6mL of tetraethyl silicate, mechanically stirring for 2h at 400r/min, then adding 1.5mL of 3- (methacryloyl) propyl trimethoxysilane, mechanically stirring for 12h at 400r/min, centrifuging to obtain a reactant, washing for 3 times by using absolute ethanol, and drying for 8h in vacuum at 60 ℃ to obtain a product a.
S2, dispersing 1 g of the product a prepared in the step S1 into 250mL of acetonitrile, adding 2mL of divinylbenzene, 2mL of styrene and 0.08g of 2, 2-azobisisobutyronitrile, reacting for 3.5h under the reflux condition, then 6000r/min, centrifuging for 8min, centrifuging out the reactant, washing for 3 times by using absolute ethyl alcohol, and drying for 8h under vacuum at 60 ℃ to obtain a product b.
And S3, dispersing 1 g of the product b prepared in the step S2 into 70mL of absolute ethyl alcohol, adding 70mL of hydrofluoric acid solution with the mass concentration of 1% to react for 80min, then carrying out centrifugation for 8min at 8000r/min to obtain a reactant, washing for 5 times by using the absolute ethyl alcohol, and carrying out vacuum drying for 8h at 60 ℃ to obtain a product c.
S4, dispersing 1 g of the product c prepared in the step S3 into 235mL of toluene, adding 2.5mL of 3-aminopropyltrimethoxysilane, reacting for 12h under the reflux condition, then carrying out centrifugation for 8min at 8000r/min, centrifuging out the reactant, washing for 3 times by using absolute ethyl alcohol, and carrying out vacuum drying for 8h at 60 ℃ to obtain a product d.
S5, dispersing 1 g of the product d prepared in the step S4 into 82mL of chloroform, carrying out ice bath until the temperature is 0 ℃, and then dropwise adding 0.82mL of chlorosulfonic acid. Then the temperature is increased to 45 ℃ for reaction for 2h. Centrifuging for 8min at 8000r/min after reaction, centrifuging to obtain a reactant, washing for 3 times by using absolute ethyl alcohol, and drying for 8h in vacuum at 60 ℃ to obtain a product e: bell type zwitterionic microballoons.
S6, 1 g of the product e prepared in the step S5: and dispersing the bell-type zwitter-ion microspheres into 250mL of acetic acid with the mass concentration of 2%, and performing ultrasonic treatment for 30min at room temperature to obtain a solution f.
S7, dissolving 10 g of chitosan in 300mL of acetic acid with the mass concentration of 20%, and reacting at 80 ℃ until the chitosan is completely dissolved to obtain a solution g.
And S8, mixing and stirring the solution f prepared in the step S6 and the solution g prepared in the step S7 at 80 ℃ for 2h to obtain a mixed solution h.
And S9, casting the mixed solution h prepared in the step S8 on a glass plate, and drying at room temperature to obtain a product i.
S10, putting the product i prepared in the step S9 into sulfuric acid with the concentration of 2M for soaking for 24h, washing with deionized water until a washing solution is neutral, and performing vacuum drying at room temperature to obtain the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity, wherein the proton conductivity and the oxidation stability are respectively shown in tables 1 and 2.
Example 3
S1, adding 100mL of ethanol, 11mL of water and 2.0mL of ammonium hydroxide into a reactor, mechanically stirring for 1h at 400r/min, then adding 6mL of tetraethyl silicate, mechanically stirring for 2h at 400r/min, then adding 1.5mL of 3- (methacryloyl) propyl trimethoxysilane, mechanically stirring for 12h at 400r/min, centrifuging to obtain a reactant, washing for 3 times by using absolute ethanol, and drying for 8h in vacuum at 60 ℃ to obtain a product a.
S2, dispersing 1 g of the product a prepared in the step S1 into 250mL of acetonitrile, adding 2mL of divinylbenzene, 2mL of styrene and 0.08g of 2, 2-azobisisobutyronitrile, reacting for 3.5h under reflux, centrifuging out the reaction product, washing with absolute ethyl alcohol for 3 times, and drying in vacuum at 60 ℃ for 8h to obtain a product b.
And S3, dispersing 1 g of the product b prepared in the step S2 into 70mL of absolute ethyl alcohol, adding 70mL of hydrofluoric acid solution with the mass concentration of 1% to react for 80min, centrifuging to obtain a reactant, washing for 5 times by using the absolute ethyl alcohol, and drying for 8h in vacuum at 60 ℃ to obtain a product c.
S4, dispersing 1 g of the product c prepared in the step S3 into 235mL of toluene, adding 2.5mL of 3-aminopropyltrimethoxysilane, reacting for 12h under the reflux condition, then centrifuging out the reactant, washing 3 times with absolute ethyl alcohol, and drying for 8h in vacuum at 60 ℃ to obtain a product d.
S5, dispersing 1 g of the product d prepared in the step S4 into 82mL of trichloromethane, carrying out ice bath to 0 ℃, and then dropwise adding 0.82mL of chlorosulfonic acid. Then the temperature is increased to 60 ℃ for reaction for 2h. Centrifuging out the reactant after the reaction, washing the reactant for 3 times by using absolute ethyl alcohol, and drying the reactant for 8 hours in vacuum at the temperature of 60 ℃ to obtain a product e: bell type zwitterionic microspheres.
S6, 1 g of the product e prepared in the step S5: and dispersing the bell-type zwitterionic microspheres into 250mL of 2 mass percent acetic acid, and performing ultrasonic treatment at room temperature for 30min to obtain a solution f.
S7, dissolving 10 g of chitosan in 300mL of acetic acid with the mass concentration of 20%, and reacting at 80 ℃ until the chitosan is completely dissolved to obtain a solution g.
And S8, mixing and stirring the solution f prepared in the step S6 and the solution g prepared in the step S7 at 80 ℃ for 2h to obtain a mixed solution h.
And S9, casting the mixed solution h prepared in the step S8 on a glass plate, and drying at room temperature to obtain a product i.
S10, putting the product i prepared in the step S9 into sulfuric acid with the concentration of 2M for soaking for 24h, washing with deionized water until a washing solution is neutral, and performing vacuum drying at room temperature to obtain the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity, wherein the proton conductivity and the oxidation stability are respectively shown in tables 1 and 2.
Comparative example 1
Substantially the same as the preparation process of example 1, except that step S5 is omitted.
Comparative example 2
The procedure of example 1 was followed except that 3.75mL of 3-aminopropyltrimethoxysilane was added in step S4 and step S5 was omitted.
Comparative example 3
Substantially the same as the preparation process of example 1, except that step S4 is omitted.
Comparative example 4
The preparation process was substantially the same as that of example 1, except that a hydrofluoric acid solution having a mass concentration of 40% was added in step S3, and step S4 was omitted.
Comparative example 5
The synthesis method of the chitosan membrane without adding microspheres is the same as that of step S7 in example 1.
The membranes obtained in examples 1 to 3 and comparative examples 1 to 5 were subjected to proton conductivity test. And (4) calculating by an alternating current impedance method. The test was carried out with an electrochemical workstation (ParStat MC 1000) at 85 ℃ and 100% relative humidity. The results are shown in the following table.
TABLE 1
[1]Experimental groups [2]Proton conductivity (mS cm-1)
[3]Example 1 [4]28.46
[5]Example 2 [6]35.46
[7]Example 3 [8]40.35
[9]Comparative example 1 [10]16.06
[11]Comparative example 2 [12]23.08
[13]Comparative example 3 [14]26.29
[15]Comparative example 4 [16]24.84
[17]Comparative example 5 [18]23.33
As can be seen from the above table, the proton conductivity of the hybrid membrane prepared by the present invention is higher than that of comparative examples 1 to 5. The microsphere synthesized in the process has a bell-type structure and an acid-base bifunctional group, and the hybrid membrane prepared by adding the microsphere into chitosan has high proton conductivity.
The oxidation stability test was performed using the films obtained in examples 1 to 3 and comparative examples 1 to 5. The weight loss of the sample membrane was calculated by soaking the membrane in a FENTON (2ppmFeSO4, 3% H2O2) reagent for 1h at 80 ℃. The results of the measurements are shown in the following table.
TABLE 2
[19]Experimental groups [20]Loss of massLoss rate and ratio (wt%)
[21]Example 1 [22]2.62
[23]Example 2 [24]2.21
[25]Example 3 [26]2.60
[27]Comparative example 1 [28]5.44
[29]Comparative example 2 [30]10.82
[31]Comparative example 3 [32]3.44
[33]Comparative example 4 [34]6.91
[35]Comparative example 5 [36]3.16
As can be seen from the above table, the mass loss rate of the bell-type zwitterionic microsphere chitosan hybrid membrane prepared by the process of the invention is obviously lower than that of the comparative examples 1-5. The attraction effect of the double bell-shaped microspheres and the chitosan chain segment inhibits the migration of the macromolecular chain, so the hybrid membrane prepared by the process is favorable for improving the oxidation stability of the membrane.
The above description should not be taken as limiting the invention to the specific embodiments, but rather, as will be readily apparent to those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined in the claims appended hereto.

Claims (10)

1. The preparation method of the bell-type zwitter-ion microsphere chitosan hybrid membrane with high proton conductivity comprises the following steps:
(1) Adding ethanol, water and ammonium hydroxide into a reactor, mechanically stirring, adding tetraethyl silicate, mechanically stirring, adding 3- (methacryloyl) propyl trimethoxy silane, mechanically stirring, centrifuging to obtain a reactant, washing with absolute ethanol, and vacuum drying to obtain a product a;
(2) Dispersing the product a prepared in the step (1) into acetonitrile, then adding divinylbenzene, styrene and 2, 2-azobisisobutyronitrile, reacting under a reflux condition, then centrifuging out reactants, and washing with absolute ethyl alcohol to obtain a product b;
(3) Dispersing the product b prepared in the step (2) into absolute ethyl alcohol, adding a hydrofluoric acid solution, centrifuging to obtain a reactant after reaction, washing with absolute ethyl alcohol, and drying in vacuum to obtain a product c;
(4) Dispersing the product c prepared in the step (3) into toluene, adding 3-aminopropyltrimethoxysilane, reacting under a reflux condition, centrifuging to obtain a reactant, washing with absolute ethyl alcohol, and drying in vacuum to obtain a product d;
(5) Dispersing the product d prepared in the step (4) into trichloromethane, dropwise adding chlorosulfonic acid, centrifuging to obtain a reactant after reaction, washing with absolute ethyl alcohol, and drying in vacuum to obtain a product e: bell-type zwitterionic microspheres;
(6) And (3) mixing the product e prepared in the step (5): dispersing bell-type zwitterionic microspheres into acetic acid to obtain a solution f;
(7) Dissolving chitosan in acetic acid to obtain a solution g;
(8) Mixing and stirring the solution f prepared in the step (6) and the solution g prepared in the step (7) to obtain a mixed solution h;
(9) Casting the mixed solution h prepared in the step (8) on a glass plate, and drying to obtain a product i;
(10) And (4) soaking the product i prepared in the step (9) in sulfuric acid, washing with deionized water until a washing solution is neutral, and drying in vacuum to obtain the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity.
2. The preparation method of the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity as claimed in claim 1, wherein the ratio of the raw materials selected in step (1) is as follows: adding 100-120mL of ethanol, 10-13mL of water and 2-2.5mL of ammonium hydroxide into a reactor, and mechanically stirring at the speed of 350-450r/min for 20 min-1 h; adding 5-8mL tetraethyl silicate in proportion, and mechanically stirring at the speed of 350-450r/min for 2-12h; adding 1-3mL of 3- (methacryloyl) propyl trimethoxy silane according to the proportion, wherein the mechanical stirring speed is 350-450r/min, the time is 12h, and the reaction temperature conditions are room temperature; the centrifugation condition is 8000r/min, the time is 8min, and then the vacuum drying is carried out, the temperature is 50-60 ℃, and the drying time is 8-24h.
3. The method for preparing the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity as claimed in claim 1, wherein in step (2), each gram of the product a corresponds to 200-250mL of acetonitrile, 1.0-2.0mL of divinylbenzene, 1.0-2.0mL of styrene and 0.05-1.0g of 2, 2-azobisisobutyronitrile, the reaction time is 3.5h under reflux condition, the centrifugation condition is 6000r/min and the time is 8min, and then the membrane is dried in vacuum at the temperature of 50-60 ℃ and the drying time is 8-24h.
4. The preparation method of the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity as claimed in claim 1, wherein in the step (3), each gram of the product b corresponds to 50-80mL of solvent ethanol and 50-80mL of hydrofluoric acid solution, the mass concentration is 1%, the reaction time is 80min, the centrifugation condition is 8000r/min, the time is 8min, and then the membrane is dried in vacuum at the temperature of 50-60 ℃ for 8-24h.
5. The preparation method of the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity as claimed in claim 1, wherein each gram of the product c in step (4) corresponds to 200-250mL of toluene solvent, 2-3mL of 3-aminopropyl trimethoxy silane, the reaction time is 12h under reflux condition, the centrifugation condition is 8000r/min and the time is 8min, and then the membrane is vacuum-dried at 50-60 ℃ for 8-24h.
6. The preparation method of the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity as claimed in claim 1, wherein in the step (5), each gram of product d corresponds to 80-100mL of chloroform as a solvent, 0.8-1.0mL of chlorosulfonic acid is added dropwise after ice-bath at 0 ℃, the reaction time is 2h, the temperature condition is 30-60 ℃, the centrifugation condition is 8000 rpm and the time is 8min, and then vacuum drying is carried out at 50-60 ℃ and the drying time is 8-24h.
7. The preparation method of the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity as claimed in claim 1, wherein in the step (6), each gram of product e corresponds to 240-260mL of acetic acid, the mass concentration is 2%, the ultrasonic treatment is carried out for 30min, and the temperature is room temperature.
8. The preparation method of the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity as claimed in claim 1, wherein in step (6), each gram of product e corresponds to 10-12 g of chitosan, each gram of chitosan corresponds to 25-30mL of acetic acid with mass concentration of 20%, the reaction temperature is 80 ℃, and the reaction time is 2h.
9. The method for preparing the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity as claimed in claim 1, wherein the stirring temperature in step (8) is 80 ℃, the reaction time is 2h, and the drying condition in step (9) is room temperature.
10. The method for preparing the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity as claimed in claim 1, wherein the sulfuric acid concentration in the step (10) is 2M, the soaking time is 24h, and the drying temperature is room temperature until the quality is unchanged, so as to obtain the bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity.
CN202211177595.9A 2022-09-27 2022-09-27 Preparation method of bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity Pending CN115558169A (en)

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