CN111276724A - Half-interpenetrating network anion exchange membrane based on polyphenyl ether/polyvinyl alcohol and preparation method thereof - Google Patents
Half-interpenetrating network anion exchange membrane based on polyphenyl ether/polyvinyl alcohol and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a semi-interpenetrating network anion exchange membrane based on polyphenyl ether/polyvinyl alcohol and a preparation method thereof. The raw materials of polyphenyl ether and polyvinyl alcohol used in the preparation process are both environment-friendly materials, and the cost is low. The fuel cell performance of the membrane has the following advantages: 1. the mechanical property is good, the tensile strength can reach 30.8MPa at most, and the elongation at break can reach 60% at most; 2. the conductivity is high, and can reach 63mS/cm at 80 ℃, which is higher than most anion exchange membranes; 3. the dimensional stability is good, and the water absorption-swelling ratio is not more than 70% at 80 ℃; 4. the alkali resistance is good, and the conductivity can still be kept at the original 67 percent after the solution is soaked in 1M NaOH aqueous solution for 500 hours at the temperature of 80 ℃.
Description
Technical Field
The invention belongs to the field of alkaline anion exchange membranes, relates to a semi-interpenetrating network anion exchange membrane based on polyphenyl ether/polyvinyl alcohol and a preparation method thereof, and particularly relates to a method for preparing a semi-interpenetrating cross-linked network by utilizing mercaptan-alkene click chemistry.
Background
In recent years, with the exhaustion of fossil energy and the increasing environmental problems, clean energy has received much attention. Among them, fuel cells have become a research hotspot of researchers as an environment-friendly power generation device. It can convert chemical energy into electric energy efficiently through electrochemical reaction without limitation of Carnot cycle.
Fuel cells have been developed for many years, and their technologies are becoming mature and their types are becoming perfect, and they can be classified into five types according to the difference of electrolytes: an Alkaline Fuel Cell (AFC), a Polymer Electrolyte Membrane Fuel Cell (PEMFC), a Phosphoric Acid Fuel Cell (PAFC), a Molten Carbonate Fuel Cell (MCFC), and a Solid Oxide Fuel Cell (SOFC), and besides, a device using methanol as fuel is called a Direct Methanol Fuel Cell (DMFC). Fuel cells can also be classified into Proton Exchange Membrane Fuel Cells (PEMFC) and Anion Exchange Membrane Fuel Cells (AEMFC) according to the type of ion exchange membrane used. Among them, Proton Exchange Membrane Fuel Cells (PEMFCs) are the earliest membrane fuel cells studied, and have the advantages of fast energy conversion, high energy conversion density, and the like. The expensive material costs, the use of noble metal catalysts, and the complex water management have hindered the large area commercial application of proton exchange membranes. Researchers have therefore turned their research direction to alkaline anion exchange membrane fuel cells, which are similar to proton exchange membrane fuel cells, with the main difference that the solid electrolyte is alkaline, relying on OH-From cathode to anode, with H+The transmission direction is opposite, the reaction kinetics is good, and a noble metal catalyst is not needed, so that the use cost of the battery is greatly reduced. With the advocation of green environmental protection concept and the adjustment of energy structure in recent years, the development of the fuel cell industry is rapidly promoted, so that the preparation of the anion exchange membrane with high ionic conductivity and good alkali resistance becomes the focus of the research in the field of the fuel cell in the future. However, anion exchange membranes are starting to be late compared to proton exchange membranes and there are still two challenges: low ionic conductivity and durabilityThe basicity is poor. OH group-Diffusion coefficient in water is only H+This greatly limits the improvement in ion conductivity of anion exchange membranes, and researchers often use methods to increase Ion Exchange Capacity (IEC) to increase ion conductivity, but too high IEC can cause the membrane to absorb water excessively, thereby affecting mechanical properties. In addition to this, the high temperature and high alkaline conditions of use (pH) of anion exchange membranes>14, 80 ℃) is required to have good alkali resistance, and researchers have carried out systematic research on polymer main chains, functional groups, structures and the like. Polyaryletherketones (PAEK), Polybenzimidazoles (PBI), Polystyrenes (PS), polyphenylene oxides (PPO), Polyarylethersulfones (PAES), polyvinyl alcohols (PVA), polyvinylidene fluorides (PVDF), and the like have been widely used for the main chain of anion exchange membranes, and quaternary amines, imidazoles, guanidino groups, quaternary phosphonium, N-spiro ammonium, and the like are generally used as functional groups. In order to prepare the anion exchange membrane with good alkali resistance and high conductivity, structures such as covalent crosslinking, semi-interpenetrating networks, comb shapes, organic-inorganic hybridization and the like are applied to the research of the exchange membrane.
Semi-interpenetrating polymer networks (sIPN) comprise one or more networks and one or more linear or branched polymers, the linear or branched polymers constituting the semi-interpenetrating network can in principle be separated from the polymer network without breaking chemical bonds. The anion exchange membrane which singly uses engineering plastics such as polyphenyl ether and the like as a main chain generally has the defects of brittleness, serious reduction of mechanical properties under an alkaline condition and the like, but the characteristics of each component in the system can be fully utilized by introducing a semi-interpenetrating polymer network structure, so that the processability and the dimensional stability of the polymer are improved.
Hao et al (sep. purif. technol.2019,211,481-490.) prepared a cross-linked anion exchange membrane by a click chemistry method, but the resulting membrane was brittle and had a low elongation at break due to the high rigidity of the polyphenylene ether component, and was susceptible to damage during use. CN 109616689A discloses a preparation method of a cross-linked anion exchange membrane, wherein an imidazole ionizing reagent is used for grafting a modified polymer main chain, and polyvinyl alcohol is added for cross-linking after film formation. However, this method uses heterogeneous membrane formation and cannot determine the degree of crosslinking.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a semi-interpenetrating network anion exchange membrane based on polyphenyl ether/polyvinyl alcohol and a preparation method thereof, which solve the problems of poor membrane flexibility and poor alkali resistance in the prior art.
Technical scheme
A semi-interpenetrating network anion exchange membrane based on polyphenyl ether/polyvinyl alcohol is characterized by comprising the following components: an imidazolium-functionalized polyphenylene ether, a polyvinyl alcohol, and a crosslinker; the mass ratio of the polyphenyl ether to the polyvinyl alcohol is 9-6: 1-4; the cross-linking agent accounts for 1-15% of the total mass of the system; the structural formula is as follows:
wherein: n represents the absolute number of repeating units in the polymer chain, X-Is Br-(ii) a R is straight chain alkane with 2-16 carbon atoms, and other C, H, O, N respectively represent carbon, hydrogen, oxygen and nitrogen elements.
A method for preparing the semi-interpenetrating network anion exchange membrane based on the polyphenyl ether/polyvinyl alcohol is characterized by comprising the following steps:
step 1: stirring and dissolving polyphenyl ether in a solvent, heating to 40-80 ℃, and adding an initiator and a bromomethylation reagent after dissolving; heating and refluxing under the protection of inert gas; after the reaction is carried out for 3-5h, pouring the reaction solution into ethanol at room temperature, repeatedly washing and drying the obtained polymer; the dosage of the initiator is 0.5-5 wt%; the bromomethylation reagent is N-bromosuccinimide, and the using amount is 15-50% by weight;
step 2: dissolving a polymer in dimethyl sulfoxide, adding 1-vinyl imidazole, stirring at 40-70 ℃ for reaction for 12-24 hours, repeatedly washing and drying to obtain the polymer; the dosage of the 1-vinyl imidazole is 5-50% of the total mass of the solution;
and step 3: dissolving the polymer and the linear polymer prepared in the step 2 in a high-boiling-point solvent, adding a cross-linking agent and a photoinitiator, stirring, casting the solution on a horizontal glass plate, exposing the horizontal glass plate to ultraviolet light for 5-20 min for click reaction crosslinking, and placing the solution in an oven for heat treatment after crosslinking to obtain an anion exchange membrane; the mass ratio of the polymer to the linear polymer is 9-6: 1-4, the amount of the cross-linking agent is 1-15% of the total mass of the solution, the heat treatment temperature is 60-80 ℃, and the heat treatment time is 24-48 hours.
The initiator comprises an organic peroxide initiator or an azo initiator.
The solvent in the step 1 is a solvent capable of completely dissolving the polyphenyl ether, the brominating agent and the initiator, and comprises benzene or chlorobenzene.
The high boiling point solvents include, but are not limited to: one or more than two of N, N-dimethylformamide DMF and N-methylpyrrolidone NMP.
The photoinitiator comprises 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone or 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone or 2-hydroxy-2-methyl-1-phenyl-1-acetone.
The ultraviolet light is 365 nm.
Soaking the anion exchange membrane in 1-2mol/L sodium hydroxide or potassium hydroxide solution, taking out after 24-48 hours, washing with deionized water for multiple times, and drying to obtain the hydroxyl type semi-interpenetrating network anion exchange membrane.
Advantageous effects
The invention provides a polyphenylene oxide/polyvinyl alcohol-based semi-interpenetrating network anion exchange membrane and a preparation method thereof, wherein a polyphenylene oxide (PPO) cross-linked structure is efficiently prepared by utilizing ultraviolet light-initiated mercaptan-alkene click chemistry, and the semi-interpenetrating network anion exchange membrane is prepared by introducing linear high molecular polyvinyl alcohol (PVA). The raw materials of polyphenyl ether and polyvinyl alcohol used in the preparation process are both environment-friendly materials, and the cost is low. The fuel cell performance of the membrane has the following advantages: 1. the mechanical property is good, the tensile strength can reach 30.8MPa at most, and the elongation at break can reach 60% at most; 2. the conductivity is high, and can reach 63mS/cm at 80 ℃, which is higher than most anion exchange membranes; 3. the dimensional stability is good, and the water absorption-swelling ratio is not more than 70% at 80 ℃; 4. the alkali resistance is good, and the conductivity can still be kept at the original 67 percent after the solution is soaked in 1M NaOH aqueous solution for 500 hours at the temperature of 80 ℃.
The invention prepares an anion exchange membrane of a semi-interpenetrating network, introduces a cross-linking structure through mercaptan-alkene click reaction, and adds polyvinyl alcohol to form the semi-interpenetrating network structure while cross-linking. Polyphenylene oxide has excellent mechanical properties and good thermal stability, and is an important raw material for preparing anion exchange membranes. The anion exchange membrane obtained by the invention has high ionic conductivity, low swelling ratio at high temperature, stability tested at 80 ℃ in 1M NaOH solution, conductivity which can keep 67 percent of the initial value, good alkali resistance and good application prospect in the field of fuel cells.
The invention provides a semi-interpenetrating network anion exchange membrane and a preparation method thereof. The method not only improves the flexibility and the ionic conductivity of the membrane, but also obviously reduces the swelling of the membrane in water, and the prepared anion exchange membrane has good application prospect in the field of fuel cells.
Drawings
FIG. 1 shows the NMR spectrum of a polymer.
FIG. 2 is an optical photograph of the prepared semi-interpenetrating network anion exchange membrane.
FIG. 3 is a Fourier transform infrared spectrum before and after cross-linking of a semi-interpenetrating anion exchange membrane.
FIG. 4 is a thermogravimetric analysis curve of the prepared semi-interpenetrating network anion exchange membrane.
FIG. 5 is a graph of the mechanical properties of the prepared semi-interpenetrating network anion exchange membrane.
FIG. 6 is a graph of temperature-conductivity relationship for a prepared semi-interpenetrating network anion exchange membrane.
FIG. 7 is a graph of conductivity versus time under alkaline immersion conditions for prepared semi-interpenetrating network anion exchange membranes.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
example 1
Dissolving a certain amount of polyphenyl ether in chlorobenzene under the condition of stirring, slowly heating to 80 ℃ under the protection of nitrogen, adding 40 wt% of N-bromosuccinimide and 2, 2' -azobisisobutyronitrile (the amount is 0.5% of the mass of the polyphenyl ether) after the polyphenyl ether is completely dissolved, uniformly stirring, and heating for 3 hours under the condition of reflux. After cooling, the reaction mixture was transferred to a beaker and washed several times with ethanol. The polymer was collected and dried in vacuo to give bromomethylated polyphenylene ether (BPPO).
Bromomethylated polyphenylene ether (BPPO) was dissolved in a solution of N-methylpyrrolidone (NMP) containing 20% wt of vinylimidazole and reacted at 70 ℃ for 12 hours. The resulting solution was precipitated by pouring into ethanol, the product was redissolved and washed with ethanol several times, and the polymer was collected and vacuum-dried to obtain an imidazole-functionalized polyphenylene ether (VIm-PPO).
Dissolving the prepared imidazole functionalized polyphenylene ether (VIm-PPO) in dimethyl sulfoxide (DMSO), adding 1, 8-octanedithiol (5 wt%) and a photoinitiator (1 wt%) into a dimethyl sulfoxide (DMSO) solution in which polyvinyl alcohol (PVA) is dissolved, wherein the mass ratio of the imidazole functionalized polyphenylene ether (VIm-PPO) to the polyvinyl alcohol is 9: 1. after stirring well, the solution was cast on a horizontal glass plate and exposed to ultraviolet light (365nm) for 10min for click reaction crosslinking. And (3) carrying out heat treatment on the membrane casting solution at 80 ℃ for 24 hours, soaking the membrane casting solution in 1M NaOH for 24 hours, and then washing the membrane casting solution with deionized water for multiple times until the membrane casting solution is neutral to obtain the semi-interpenetrating network anion exchange membrane.
The determination shows that the membrane is insoluble in water, the water absorption rate of the membrane at room temperature is 41.6%, the ion exchange capacity is 1.46mmol/g, the conductivity in an aqueous solution is 26mS/cm, the conductivity is in positive correlation with the temperature, and the hydroxide ion conductivity at 80 ℃ can reach 63 mS/cm. The bromomethylated polyphenylene ether and imidazole-functionalized polyphenylene ether were structurally characterized using a nuclear magnetic resonance spectrometer, and the results are shown in FIG. 1. The two peaks at 4.3 and 2.24ppm are the brominated methylene proton and the methyl hydrogen atom, and the peaks at 8.13 and 9.32ppm are the hydrogen atoms of the imidazole ring, indicating the successful preparation of bromomethylated polyphenylene ethers and imidazole functionalized polyphenylene ethers.
Structural characterization is carried out on the anion exchange membrane before and after the click reaction by using a Fourier transform infrared spectrometer, and the result is shown in figure 3, compared with the uncrosslinked membrane, 1639cm-1(C ═ C group) and 909cm-1The disappearance of the two absorption peaks at (═ C-H) further indicates the successful progress of the thiol-ene click reaction and that the polymer has formed a covalently crosslinked network.
A thermal weight loss analyzer is used for representing the thermal stability of the cross-linked anion exchange membrane, a membrane sample to be tested is tested in a nitrogen atmosphere, the temperature rise rate is 10 ℃/min, the temperature range is 35-800 ℃, and the test result is shown in figure 4, which shows that the prepared membrane has good thermal stability at the use temperature (80 ℃) of a fuel cell.
The mechanical properties of the cross-linked anion exchange membrane are characterized by using a universal tensile tester, the membrane is cut into dumbbell-shaped samples of 1cm multiplied by 3cm for testing, the tensile rate is 1mm/min, the test result is shown in figure 5, the tensile strength exceeds 20Mpa, and the membrane has excellent mechanical properties.
The ionic conductivity of the membrane was measured at different temperatures using an electrochemical workstation and the results are shown in figure 6. The result shows that the prepared membrane has good ionic conductivity, and the hydroxide conductivity at 80 ℃ is more than 60 mS/cm.
Soaking the membrane in a 1M NaOH solution at 80 ℃, taking out the membrane at different times, measuring the ionic conductivity of the membrane at room temperature, comparing the ionic conductivity with that of the membrane which is not soaked, and representing the alkali-resistant stability of the membrane through the conductivity change before and after treatment. The test result is shown in fig. 7, after the membrane is soaked in the alkali solution for 500 hours, the conductivity can still keep 67% of the initial value, which indicates good alkali-resistant stability.
Example 2
Dissolving a certain amount of polyphenyl ether in chlorobenzene under the condition of stirring, slowly heating to 60 ℃ under the protection of nitrogen, adding 40 wt% of N-bromosuccinimide and 2, 2' -azobisisobutyronitrile (the amount is 0.5% of the mass of the polyphenyl ether) after the polyphenyl ether is completely dissolved, uniformly stirring, and heating for 3 hours under the condition of reflux. After cooling, the reaction mixture was transferred to a beaker and washed several times with ethanol. The polymer was collected and dried in vacuo to give bromomethylated polyphenylene ether (BPPO).
Bromomethylated polyphenylene ether (BPPO) was dissolved in a solution of N-methylpyrrolidone (NMP) containing 20% wt of vinylimidazole and reacted at 60 ℃ for 24 hours. The resulting solution was precipitated by pouring into ethanol, the product was redissolved and washed with ethanol several times, and the polymer was collected and vacuum-dried to obtain an imidazole-functionalized polyphenylene ether (VIm-PPO).
Dissolving the prepared imidazole functionalized polyphenylene ether (VIm-PPO) in dimethyl sulfoxide (DMSO), adding 1, 8-octanedithiol (5 wt%) and a photoinitiator (1 wt%) into a dimethyl sulfoxide (DMSO) solution in which polyvinyl alcohol (PVA) is dissolved, wherein the mass ratio of the imidazole functionalized polyphenylene ether (VIm-PPO) to the polyvinyl alcohol is 8: 2. after stirring well, the solution was cast on a horizontal glass plate and exposed to ultraviolet light (365nm) for 10min for click reaction crosslinking. And (3) carrying out heat treatment on the membrane casting solution at 60 ℃ for 24 hours, soaking the membrane casting solution in 1M NaOH for 24 hours, and then washing the membrane casting solution with deionized water for multiple times until the membrane casting solution is neutral to obtain the semi-interpenetrating network anion exchange membrane.
The membrane is determined to be insoluble in water, the water absorption of the membrane at room temperature is 35.9%, the ion exchange capacity is 1.34mmol/g, the conductivity in aqueous solution is 24.2mS/cm, and the conductivity is in positive correlation with the temperature.
Example 3
Dissolving a certain amount of polyphenyl ether in chlorobenzene under the condition of stirring, slowly heating to 50 ℃ under the protection of nitrogen, adding 40 wt% of N-bromosuccinimide and 2, 2' -azobisisobutyronitrile (the amount is 0.5% of the mass of the polyphenyl ether) after the polyphenyl ether is completely dissolved, stirring uniformly, and heating for 5 hours under the condition of reflux. After cooling, the reaction mixture was transferred to a beaker and washed several times with ethanol. The polymer was collected and dried in vacuo to give bromomethylated polyphenylene ether (BPPO).
Bromomethylated polyphenylene ether (BPPO) was dissolved in a solution of N-methylpyrrolidone (NMP) containing 20% by weight of vinylimidazole and reacted at 50 ℃ for 24 hours. The resulting solution was precipitated by pouring into ethanol, the product was redissolved and washed with ethanol several times, and the polymer was collected and vacuum-dried to obtain an imidazole-functionalized polyphenylene ether (VIm-PPO).
Dissolving the prepared imidazole functionalized polyphenylene ether (VIm-PPO) in dimethyl sulfoxide (DMSO), adding 1, 8-octanedithiol (5 wt%) and a photoinitiator (1 wt%) into a dimethyl sulfoxide (DMSO) solution in which polyvinyl alcohol (PVA) is dissolved, wherein the mass ratio of the imidazole functionalized polyphenylene ether (VIm-PPO) to the polyvinyl alcohol is 7: 3. after stirring well, the solution was cast on a horizontal glass plate and exposed to ultraviolet light (365nm) for 10min for click reaction crosslinking. And (3) carrying out heat treatment on the membrane casting solution at 70 ℃ for 24 hours, soaking the membrane casting solution in 1M NaOH for 24 hours, and then washing the membrane casting solution with deionized water for multiple times until the membrane casting solution is neutral to obtain the semi-interpenetrating network anion exchange membrane.
The membrane is determined to be insoluble in water, the water absorption of the membrane at room temperature is 25.9%, the ion exchange capacity is 1.26mmol/g, the conductivity in aqueous solution is 21.6mS/cm, and the conductivity is positively correlated with the temperature.
Example 4
Dissolving a certain amount of polyphenyl ether in chlorobenzene under the condition of stirring, slowly heating to 60 ℃ under the protection of nitrogen, adding 40 wt% of N-bromosuccinimide and 2, 2' -azobisisobutyronitrile (the amount is 0.5% of the mass of the polyphenyl ether) after the polyphenyl ether is completely dissolved, uniformly stirring, and heating for 4 hours under the condition of reflux. After cooling, the reaction mixture was transferred to a beaker and washed several times with ethanol. The polymer was collected and dried in vacuo to give bromomethylated polyphenylene ether (BPPO).
Bromomethylated polyphenylene ether (BPPO) was dissolved in a solution of N-methylpyrrolidone (NMP) containing 20% wt of vinylimidazole and reacted at 80 ℃ for 12 hours. The resulting solution was precipitated by pouring into ethanol, the product was redissolved and washed with ethanol several times, and the polymer was collected and vacuum-dried to obtain an imidazole-functionalized polyphenylene ether (VIm-PPO).
Dissolving the prepared imidazole functionalized polyphenylene ether (VIm-PPO) in dimethyl sulfoxide (DMSO), adding 1, 8-octanedithiol (5 wt%) and a photoinitiator (1 wt%) into a dimethyl sulfoxide (DMSO) solution in which polyvinyl alcohol (PVA) is dissolved, wherein the mass ratio of the imidazole functionalized polyphenylene ether (VIm-PPO) to the polyvinyl alcohol is 6: 4. after stirring well, the solution was cast on a horizontal glass plate and exposed to ultraviolet light (365nm) for 10min for click reaction crosslinking. And (3) carrying out heat treatment on the membrane casting solution at 60 ℃ for 24 hours, soaking the membrane casting solution in 1M NaOH for 24 hours, and then washing the membrane casting solution with deionized water for multiple times until the membrane casting solution is neutral to obtain the semi-interpenetrating network anion exchange membrane.
The membrane is determined to be insoluble in water, the water absorption rate of the membrane at room temperature is 12.6%, the ion exchange capacity is 0.78mmol/g, the conductivity in aqueous solution is 16.4mS/cm, and the conductivity is in positive correlation with the temperature.
Example 5
Dissolving a certain amount of polyphenyl ether in chlorobenzene under the condition of stirring, slowly heating to 80 ℃ under the protection of nitrogen, adding 40 wt% of N-bromosuccinimide and 2, 2' -azobisisobutyronitrile (the amount is 0.5% of the mass of the polyphenyl ether) after the polyphenyl ether is completely dissolved, uniformly stirring, and heating for 3 hours under the condition of reflux. After cooling, the reaction mixture was transferred to a beaker and washed several times with ethanol. The polymer was collected and dried in vacuo to give bromomethylated polyphenylene ether (BPPO).
Bromomethylated polyphenylene ether (BPPO) was dissolved in a solution of N-methylpyrrolidone (NMP) containing 20% wt of vinylimidazole and reacted at 60 ℃ for 24 hours. The resulting solution was precipitated by pouring into ethanol, the product was redissolved and washed with ethanol several times, and the polymer was collected and vacuum-dried to obtain an imidazole-functionalized polyphenylene ether (VIm-PPO).
Dissolving the prepared imidazole functionalized polyphenylene ether (VIm-PPO) in dimethyl sulfoxide (DMSO), and adding the prepared imidazole functionalized polyphenylene ether (VIm-PPO) into a dimethyl sulfoxide (DMSO) solution in which polyvinyl alcohol (PVA) is dissolved, wherein the mass ratio of the imidazole functionalized polyphenylene ether (VIm-PPO) to the polyvinyl alcohol is 6: 4. after being uniformly stirred, the solution is cast on a horizontal glass plate, is subjected to heat treatment at 60 ℃ for 48 hours, is soaked in 1M NaOH for 24 hours, and is washed by deionized water for multiple times until the solution is neutral, so that the hybrid anion exchange membrane is obtained.
The film is insoluble in water, the water absorption rate of the film at room temperature is 15.6%, and the film does not form a cross-linked structure, so that the mechanical strength is low, the hydroxide ion conductivity is low, and the excellent performance of the semi-interpenetrating network anion exchange film based on the polyphenyl ether/polyvinyl alcohol is proved.
Example 6
The procedure is as in example 1, except that the photoinitiator used is 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-one, and the film obtained is photocrosslinked under ultraviolet light (365nm) for 5min, and the indices of the film obtained are as in example 1.
Example 7
The procedure was as in example 1 except that the film heat treatment was carried out at 100 ℃ for 12 hours. The film obtained was rated as in example 1.
Example 8
The procedure is the same as in example 2, except that the photoinitiator used is 2-hydroxy-2-methyl-1-phenyl-1-propanone, and the film obtained is photocrosslinked under ultraviolet light (365nm) for 15min, and the indexes of the film are the same as in example 2.
Claims (8)
1. A semi-interpenetrating network anion exchange membrane based on polyphenyl ether/polyvinyl alcohol is characterized by comprising the following components: an imidazolium-functionalized polyphenylene ether, a polyvinyl alcohol, and a crosslinker; the mass ratio of the polyphenyl ether to the polyvinyl alcohol is 9-6: 1-4; the cross-linking agent accounts for 1-15% of the total mass of the system; the structural formula is as follows:
wherein: n represents the absolute number of repeating units in the polymer chain, X-Is Br-(ii) a R is straight chain alkane with 2-16 carbon atoms, and other C, H, O, N respectively represent carbon, hydrogen, oxygen and nitrogen elements.
2. A process for preparing a polyphenylene ether/polyvinyl alcohol based semi-interpenetrating network anion exchange membrane of claim 1, characterized by the steps of:
step 1: stirring and dissolving polyphenyl ether in a solvent, heating to 40-80 ℃, and adding an initiator and a bromomethylation reagent after dissolving; heating and refluxing under the protection of inert gas; after the reaction is carried out for 3-5h, pouring the reaction solution into ethanol at room temperature, repeatedly washing and drying the obtained polymer; the dosage of the initiator is 0.5-5 wt%; the bromomethylation reagent is N-bromosuccinimide, and the using amount is 15-50% by weight;
step 2: dissolving a polymer in dimethyl sulfoxide, adding 1-vinyl imidazole, stirring at 40-70 ℃ for reaction for 12-24 hours, repeatedly washing and drying to obtain the polymer; the dosage of the 1-vinyl imidazole is 5-50% of the total mass of the solution;
and step 3: dissolving the polymer and the linear polymer prepared in the step 2 in a high-boiling-point solvent, adding a cross-linking agent and a photoinitiator, stirring, casting the solution on a horizontal glass plate, exposing the horizontal glass plate to ultraviolet light for 5-20 min for click reaction crosslinking, and placing the solution in an oven for heat treatment after crosslinking to obtain an anion exchange membrane; the mass ratio of the polymer to the linear polymer is 9-6: 1-4, the amount of the cross-linking agent is 1-15% of the total mass of the solution, the heat treatment temperature is 60-80 ℃, and the heat treatment time is 24-48 hours.
3. The method of claim 2, wherein: the initiator comprises an organic peroxide initiator or an azo initiator.
4. The method of claim 2, wherein: the solvent in the step 1 is a solvent capable of completely dissolving the polyphenyl ether, the brominating agent and the initiator, and comprises benzene or chlorobenzene.
5. The method of claim 2, wherein: the high boiling point solvents include, but are not limited to: one or more than two of N, N-dimethylformamide DMF and N-methylpyrrolidone NMP.
6. The method of claim 2, wherein: the photoinitiator comprises 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone or 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone or 2-hydroxy-2-methyl-1-phenyl-1-acetone.
7. The method of claim 2, wherein: the ultraviolet light is 365 nm.
8. The method of claim 2, wherein: soaking the anion exchange membrane in 1-2mol/L sodium hydroxide or potassium hydroxide solution, taking out after 24-48 hours, washing with deionized water for multiple times, and drying to obtain the hydroxyl type semi-interpenetrating network anion exchange membrane.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112201827A (en) * | 2020-09-21 | 2021-01-08 | 安徽师范大学 | Preparation method of novel composite proton exchange membrane material |
| CN112717732A (en) * | 2020-12-29 | 2021-04-30 | 太原理工大学 | Amino-rich doped polysuccinimide semi-interpenetrating network blending membrane and preparation method and application thereof |
| CN114695933A (en) * | 2022-03-10 | 2022-07-01 | 武汉轻工大学 | Semi-interpenetrating anion exchange membrane and preparation method and application thereof |
| CN115312971A (en) * | 2022-08-18 | 2022-11-08 | 江阴纳力新材料科技有限公司 | Polymer film, preparation method thereof and composite current collector |
| CN115926425A (en) * | 2022-12-14 | 2023-04-07 | 武汉轻工大学 | Cross-linked anion exchange membrane and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5855008A (en) * | 1981-09-29 | 1983-04-01 | Mitsubishi Chem Ind Ltd | Separating membrane for gas |
| JP2007273203A (en) * | 2006-03-31 | 2007-10-18 | National Institute Of Advanced Industrial & Technology | Cross-linking type polymer electrolyte membrane |
| CN104941468A (en) * | 2015-05-29 | 2015-09-30 | 厦门大学 | Semi-interpenetrating network anion exchange membrane and production method thereof |
| CN105406097A (en) * | 2014-09-16 | 2016-03-16 | 张宏伟 | Ultra-thin solid electrolyte film and preparation method thereof |
| CN109904501A (en) * | 2019-01-17 | 2019-06-18 | 湖北工程学院 | Compound alkaline polyelectrolyte film of one kind and its preparation method and application |
| CN110137550A (en) * | 2019-05-28 | 2019-08-16 | 西北工业大学 | A kind of alkaline anion-exchange membrane and preparation method and formates fuel cell preparation method |
| CN110760038A (en) * | 2019-11-18 | 2020-02-07 | 长春工业大学 | Imidazole side chain type anion exchange membrane for fuel cell and preparation method thereof |
-
2020
- 2020-02-15 CN CN202010094147.7A patent/CN111276724B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5855008A (en) * | 1981-09-29 | 1983-04-01 | Mitsubishi Chem Ind Ltd | Separating membrane for gas |
| JP2007273203A (en) * | 2006-03-31 | 2007-10-18 | National Institute Of Advanced Industrial & Technology | Cross-linking type polymer electrolyte membrane |
| CN105406097A (en) * | 2014-09-16 | 2016-03-16 | 张宏伟 | Ultra-thin solid electrolyte film and preparation method thereof |
| CN104941468A (en) * | 2015-05-29 | 2015-09-30 | 厦门大学 | Semi-interpenetrating network anion exchange membrane and production method thereof |
| CN109904501A (en) * | 2019-01-17 | 2019-06-18 | 湖北工程学院 | Compound alkaline polyelectrolyte film of one kind and its preparation method and application |
| CN110137550A (en) * | 2019-05-28 | 2019-08-16 | 西北工业大学 | A kind of alkaline anion-exchange membrane and preparation method and formates fuel cell preparation method |
| CN110760038A (en) * | 2019-11-18 | 2020-02-07 | 长春工业大学 | Imidazole side chain type anion exchange membrane for fuel cell and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| WU YONGHUI 等: ""QPPO/PVA anion exchange hybrid membranes from double crosslinking agents for acid recovery"", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| 刘雅芝等: ""面向燃料电池的聚苯醚基离子交换膜"", 《高分子学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112201827A (en) * | 2020-09-21 | 2021-01-08 | 安徽师范大学 | Preparation method of novel composite proton exchange membrane material |
| CN112717732A (en) * | 2020-12-29 | 2021-04-30 | 太原理工大学 | Amino-rich doped polysuccinimide semi-interpenetrating network blending membrane and preparation method and application thereof |
| CN114695933A (en) * | 2022-03-10 | 2022-07-01 | 武汉轻工大学 | Semi-interpenetrating anion exchange membrane and preparation method and application thereof |
| CN114695933B (en) * | 2022-03-10 | 2023-12-22 | 武汉轻工大学 | Semi-interpenetrating anion exchange membrane and preparation method and application thereof |
| CN115312971A (en) * | 2022-08-18 | 2022-11-08 | 江阴纳力新材料科技有限公司 | Polymer film, preparation method thereof and composite current collector |
| CN115926425A (en) * | 2022-12-14 | 2023-04-07 | 武汉轻工大学 | Cross-linked anion exchange membrane and preparation method thereof |
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