CN118978729A - Polyarylalkyl cross-linked modified polybenzimidazole anion exchange membrane and preparation method and application thereof - Google Patents
Polyarylalkyl cross-linked modified polybenzimidazole anion exchange membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polyaromatic alkyl crosslinking modified polybenzimidazole anion exchange membrane, a preparation method and application thereof. By crosslinking modified polybenzimidazole modified by ion conducting groups containing long alkyl side chains with a polyaromatic alkyl polymer with haloalkane side chains and then casting the film, a high-performance anion exchange film with a definite hydrophilic/hydrophobic microphase separation structure is designed. The prepared membrane has good dimensional stability and higher ion conductivity, and can be applied to an anion exchange membrane water electrolysis tank and an alkaline fuel cell.
Description
Technical Field
The invention relates to a preparation method and application of a polyarylalkyl cross-linked modified polybenzimidazole anion exchange membrane, and belongs to the technical field of anion exchange membranes.
Background
Hydrogen energy technology and application and renewable energy source hydrogen production are encouraging industrial directions in China. The hydrogen produced by renewable energy sources is also called green hydrogen, and compared with the traditional hydrogen energy source production mode, the hydrogen produced by renewable energy sources realizes zero carbon emission in the preparation process, so that the hydrogen produced by renewable energy sources is also called the purest green energy sources. Hydrogen production from alkaline water is an important mode of green hydrogen production, and an anion exchange membrane is one of the core components of an electrolyzer for producing hydrogen from alkaline water. The development of anion exchange membranes mainly faces the problems of low ionic conductivity and poor mechanical properties. In order to increase the conductivity, it is generally required that the anion exchange membrane has a higher Ion Exchange Capacity (IEC), which can be achieved by increasing the density of ionic groups within the membrane, thereby forming efficient ion transport channels, but this leads to an increase in the water absorption swelling of the membrane, thereby reducing the dimensional stability and mechanical properties of the anion exchange membrane. The use of several polymers with different mechanical properties to crosslink to form a continuous ion channel can solve this problem. Patent publication No. CN117964932A discloses an interpenetrating network anion exchange membrane of polysulfone crosslinked polybenzimidazole, which is prepared by crosslinking Polybenzimidazole (PBI) modified by long alkyl side chain ion conduction groups with modified haloalkyl substituted Polysulfone (PSF) material and then casting the membrane, thus the anion exchange membrane material with interpenetrating network structure is prepared, and the dimensional stability and mechanical property of the anion exchange membrane are improved. However, PSF as an aryl-ether polymer is susceptible to backbone degradation under alkaline conditions to produce benzylic AEMs. Aryl ether cleavage is accelerated by electron traction linkages and adjacent cationic groups, and furthermore, the benzyl position of the cationic groups may limit their local mobility, making them particularly vulnerable to nucleophilic attack. This vulnerability can lead to reduced hydroxide conductivity and rapid degradation of cationic groups.
Disclosure of Invention
The invention aims to solve the problem of poor chemical stability of the existing anion exchange membrane (such as an aryl ether polycyclic aromatic hydrocarbon polymer) in an alkaline environment, and provides a polyaromatic alkyl crosslinking modified polybenzimidazole anion exchange membrane, and a preparation method and application thereof. By crosslinking and then casting modified Polybenzimidazole (PBI) modified by ion conducting groups containing long alkyl side chains with a polyaromatic alkyl polymer having haloalkane side chains, a high performance anion exchange membrane having a well-defined hydrophilic/hydrophobic microphase separation structure is designed. The prepared membrane has good dimensional stability and higher ion conductivity, and can be applied to an anion exchange membrane water electrolysis tank and an alkaline fuel cell.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a polyarylalkyl crosslinking modified polybenzimidazole anion exchange membrane has the structure shown as follows:
wherein x and y are positive integers greater than or equal to 1, m is 1 or 2, n is 1,2 or 3, ar is the following structure:
FG + is an incorporated ion-conducting group, including N-methylalkylpiperidinium ion, trimethylalkylammonium ion, 1-methyl-3-alkylimidazolium ion.
A preparation method of a polyaromatic alkyl crosslinking modified polybenzimidazole anion exchange membrane comprises the following steps:
(1) Preparation of polyaromatic alkyl polymers
Adding different aryl monomers and carbonyl monomers with different chain lengths into Dichloromethane (DCM) under ice-water bath to dissolve and stir, dropwise adding super acid after the reactant is completely cooled, continuing ice bath for 10-60 minutes, reacting at room temperature for 2-8 hours, then dropwise adding a viscous solution into a precipitator B to obtain fibrous solid, purifying, washing and drying to synthesize the polyaromatic alkyl polymer with different side chain lengths;
(2) Preparation of crosslinked network anion exchange membranes
Dissolving modified polybenzimidazole modified by long alkyl side chain ion conduction groups and the polyaromatic alkyl polymer obtained in the step (1) in dimethyl sulfoxide (DMSO) to prepare a casting solution, reacting at 60-80 ℃, casting the casting solution on a glass plate, drying the casting solution to form a film, soaking the film in alkali liquor for ion exchange, soaking the film in deionized water to be neutral to obtain the anion exchange film with a cross-linked network structure,
The modified polybenzimidazole modified by the ion conduction group containing the long alkyl side chain has the structural formula:
X is a halogen atom such as bromine, chlorine, etc.
The invention adopts the method described in the patent with the publication number of CN117964932A to prepare the modified polybenzimidazole modified by the ion conduction group containing the long alkyl side chain. The specific method comprises the following steps: under the protection of nitrogen, different nitrogen-containing compounds are dissolved in a solvent 1, a certain equivalent of dibromide is added for reaction for 12-48 hours at 30-60 ℃, and then the white solid is obtained through suction filtration and washing with a reagent 1. Adding the white solid into a mixed solution of solvent 2 of polybenzimidazole and sodium hydride which are reacted in advance, reacting for 24-48 hours at the temperature of 80-100 ℃, pouring the reaction solution into a precipitator A, and carrying out suction filtration, washing and drying to obtain the modified polybenzimidazole modified by long alkyl side chain ion conduction groups.
The nitrogen-containing compound is N-methylpiperidine, trimethylamine and 1, 2-dimethylimidazole; the dibromide is 1, 4-dibromobutane and 1, 6-dibromohexane; the equivalent of the dibromide is 3-5 times of the equivalent of the dibromide; the addition of the white solid is 2 to 10 times, preferably 4 to 6 times, the amount of the N-H-based substance in the polybenzimidazole; solvent 1 is tetrahydrofuran, acetone, acetonitrile; the solvent 2 is N, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide; reagent 1 is diethyl ether or ethyl acetate; the precipitant A is acetone and water.
The aryl monomer in the step (1) is para-terphenyl, biphenyl, diphenyl ether and 9, 9-dimethylfluorene, and the structural formulas of the para-terphenyl, the biphenyl, the diphenyl ether and the 9, 9-dimethylfluorene are specifically as follows:
The carbonyl monomer in step (1) is 6-bromo-1, 1-trifluorohexane-2-one, 7-bromo-1, 1-trifluoroheptane-2-one. Of course, bromine in the structural formula can also be halogen elements such as chlorine, fluorine, iodine and the like.
The super acid in the step (1) is trifluoroacetic acid (TFSA) or trifluoromethanesulfonic acid.
It should be noted that: the polyaromatic alkyl polymer with different side chain lengths is synthesized after purification, washing and drying, and specifically comprises the following steps: the fibrous solid is redissolved in chloroform and precipitated in a precipitator B to obtain fibrous polymer, the fibrous polymer is repeatedly washed by the precipitator B, and finally the fibrous polymer is dried to synthesize the polyaromatic alkyl polymer with different side chain lengths. The precipitant B is water, methanol or ethanol.
The molar ratio of the polyaromatic alkyl polymer to the modified polybenzimidazole modified by the ion conducting group containing long alkyl side chain in the step (2) is in the range of 1:0.5-6.
The w/v of the casting solution in the step (2) is 3-10%.
The modified polybenzimidazole modified by the ion conduction group containing the long alkyl side chain in the step (2) reacts with the polyaromatic alkyl polymer for 0.5 to 3 hours at the temperature of 60 to 80 ℃.
The alkali liquor in the step (2) is selected from lithium hydroxide solution, sodium hydroxide solution, potassium hydroxide solution, cesium hydroxide solution or barium hydroxide solution, and the concentration range is selected from 0.2mol/L to 5mol/L, wherein the alkali liquor is preferably sodium hydroxide solution or potassium hydroxide solution, and the concentration is preferably 1mol/L to 2mol/L.
The polyarenyl crosslinking modified polybenzimidazole anion exchange membrane is applied to the fields of fuel cells, electrolytic water baths and the like.
The invention adopts a series of aryl-free frameworks which are polymerized by superacid catalysis to replace the prior PSF frameworks, and the frameworks not only have higher ionic conductivity, but also have good alkali stability.
The invention has the beneficial effects that: the anion exchange membrane of the polyaromatic alkyl crosslinking polybenzimidazole has higher ion conductivity and excellent mechanical property, and has good application prospect.
Drawings
FIG. 1 is a conductivity-temperature curve of a crosslinked film PTPA-C5-PBI-C6-Pip prepared according to the present invention.
FIG. 2 is a graph showing the water absorption vs. temperature of crosslinked films PTPA-C5-PBI-C6-Pip prepared according to the present invention.
FIG. 3 is a graph showing the swelling ratio versus temperature of the crosslinked film PTPA-C5-PBI-C6-Pip prepared according to the present invention.
FIG. 4 is a graph showing the conductivity versus time (25 ℃) of a crosslinked film PTPA-C5-PBI-C6-Pip prepared according to the present invention after immersion in 1M KOH solution.
FIG. 5 is a conductivity-time curve (25 ℃) of a crosslinked film PSF-C4-PBI-C6-Pip after immersion in 1M KOH solution.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings and technical schemes.
Example 1
(1) Synthesis of modified polybenzimidazole modified by ion conducting group containing long alkyl side chain
This example uses the method described in the patent publication No. CN117964932A to prepare polybenzimidazole PBI-C4-Pip, PBI-C6-Pip, PBI-C4-QA, PBI-C6-QA, PBI-C4-Im, PBI-C6-Im modified with a long alkyl side chain ion conducting group. The specific preparation methods are all cited below.
(101) Preparation of PBI-C4-Pip:
Under the protection of nitrogen, 20mmol of N-methylpiperidine is dissolved in acetonitrile, after being fully stirred, 100mmol of 1, 4-dibromobutane is added, and the mixture is fully stirred and reacts for 48 hours at 60 ℃, then the reaction liquid is filtered by suction, washed for a plurality of times by diethyl ether, and is placed under vacuum and dried for 24 hours at 60 ℃ to obtain the C4-Pip. Dissolving 2.5mmol of PBI material in dimethyl sulfoxide, stirring thoroughly to form 5wt.% solution, adding 10mmol of sodium hydride, reacting at room temperature for 12h, adding 10mmol of C4-Pip, reacting at 80 ℃ for 48h, separating out with acetone after the reaction is finished, washing in acetone for 3-5 times repeatedly, and drying at 60 ℃ under vacuum for 24h to obtain PBI-C4-Pip.
(102) Preparation of PBI-C6-Pip:
Under the protection of nitrogen, 20mmol of N-methylpiperidine is dissolved in acetonitrile, after being fully stirred, 100mmol of 1, 6-dibromohexane is added, and the mixture is fully stirred and reacts for 48 hours at 60 ℃, then the reaction liquid is filtered by suction, washed for a plurality of times by diethyl ether, and is placed under vacuum and dried for 24 hours at 60 ℃ to obtain the C6-Pip. Dissolving 2.5mmol of PBI material in dimethyl sulfoxide, stirring thoroughly to form 5wt.% solution, adding 10mmol of sodium hydride, reacting at room temperature for 12h, adding 10mmol of C6-Pip, reacting at 80 ℃ for 48h, separating out with acetone after the reaction is finished, washing in acetone for 3-5 times repeatedly, and drying at 60 ℃ under vacuum for 24h to obtain PBI-C6-Pip.
(103) Preparation of PBI-C4-QA:
Under the protection of nitrogen, 20mmol of trimethylamine is dissolved in acetonitrile, after being fully stirred, 100mmol of 1, 4-dibromobutane is added, and the mixture is fully stirred and reacts for 48 hours at 60 ℃, then the reaction liquid is filtered by suction, washed for a plurality of times by diethyl ether, and is placed under vacuum and dried for 24 hours at 40 ℃ to obtain the C4-QA. Dissolving 2.5mmol of PBI material in dimethyl sulfoxide, stirring thoroughly to form 5wt.% solution, adding 10mmol of sodium hydride, reacting at room temperature for 12h, then adding 10mmol of C4-QA, reacting at 100 ℃ for 24h, separating out with acetone after the reaction is finished, washing in acetone for 3-5 times repeatedly, and drying at 50 ℃ under vacuum for 36h to obtain PBI-C4-QA.
(104) Preparation of PBI-C6-QA:
Under the protection of nitrogen, 20mmol of trimethylamine is dissolved in acetonitrile, after being fully stirred, 100mmol of 1, 6-dibromohexane is added, and the mixture is fully stirred and reacts for 48 hours at 60 ℃, then the reaction liquid is filtered by suction, washed for a plurality of times by diethyl ether, and is placed under vacuum and dried for 24 hours at 40 ℃ to obtain the C6-QA. 2.5mmol of PBI material is dissolved in dimethyl sulfoxide, and is fully stirred and dissolved to form 5wt.% solution, then 10mmol of sodium hydride is added for reaction at room temperature for 12 hours, then 10mmol of C6-QA is added for reaction at 100 ℃ for 24 hours, after the reaction is finished, acetone is used for precipitation, washing is repeatedly carried out for 3-5 times in the acetone, and the solution is placed under vacuum and dried at 50 ℃ for 36 hours, thus obtaining PBI-C6-QA.
(105) Preparation of PBI-C4-Im:
Under the protection of nitrogen, 20mmol of 1, 2-dimethyl imidazole is dissolved in acetonitrile, after being fully stirred, 100mmol of 1, 4-dibromobutane is added, and the mixture is fully stirred and reacts for 48 hours at 60 ℃, then the reaction liquid is filtered by suction, washed for a plurality of times by diethyl ether, and is placed under vacuum and dried for 24 hours at 60 ℃ to obtain C4-Im. Dissolving 2.5mmol of PBI material in dimethyl sulfoxide, stirring thoroughly to form 5wt.% solution, adding 10mmol of sodium hydride, reacting at room temperature for 12h, adding 10mmol of C4-Im, reacting at 80 ℃ for 24h, precipitating with acetone after the reaction is finished, washing in acetone for 3-5 times repeatedly, and drying at 60 ℃ for 24h under vacuum to obtain PBI-C4-Im.
(106) Preparation of PBI-C6-Im:
Under the protection of nitrogen, 20mmol of 1, 2-dimethylimidazole is dissolved in acetonitrile, after being fully stirred, 100mmol of 1, 6-dibromohexane is added, and the mixture is fully stirred and reacts for 48 hours at 60 ℃, then the reaction liquid is filtered by suction, washed for a plurality of times by diethyl ether, and is placed under vacuum and dried for 24 hours at 60 ℃ to obtain C6-Im. Dissolving 2.5mmol of PBI material in dimethyl sulfoxide, stirring thoroughly to form 5wt.% solution, adding 10mmol of sodium hydride, reacting at room temperature for 12h, adding 10mmol of C6-Im, reacting at 80 ℃ for 24h, precipitating with acetone after the reaction is finished, washing in acetone for 3-5 times repeatedly, and drying at 60 ℃ for 24h under vacuum to obtain PBI-C6-Im.
(2) Polyaromatic alkyl polymers
Four polyaromatic polymers were prepared in this example, PTPA-C4, PTPA-C5, PFPA-C4 and PFPA-C5, respectively. The preparation method comprises the following steps:
(201) PTPA-C4 preparation:
2mmol of p-terphenyl and 2.2mmol of 6-bromo-1, 1-trifluoro-hexane-2-one are added into 5ml of dichloromethane to be dissolved and stirred, then the mixture is placed into an ice bath to be stirred for about ten minutes, after the reactant is completely cooled, 1.77ml of TFSA is added dropwise, and after 30 minutes of ice bath, the reaction is carried out for 6 hours at room temperature. Then, the viscous solution was dropped into methanol to obtain a fibrous solid. The polymer was redissolved in chloroform and precipitated in methanol to give a fibrous polymer which was repeatedly washed with methanol and finally dried under vacuum at 60℃for 24h to give PTPA-C4.
(202) PTPA-C5 preparation:
2mmol of p-terphenyl and 2.2mmol of 7-bromo-1, 1-trifluoro-heptane-2-ketone are added into 5ml of dichloromethane to be dissolved and stirred, then the mixture is placed into an ice bath to be stirred for about ten minutes, after the reactant is completely cooled, 1.77ml of TFSA is added dropwise, and after 30 minutes of ice bath, the reaction is carried out for 6 hours at room temperature. Then, the viscous solution was dropped into methanol to obtain a fibrous solid. The polymer was redissolved in chloroform and precipitated in methanol to give a fibrous polymer which was repeatedly washed with methanol and finally dried under vacuum at 60℃for 24h.
(203) PFPA-C4 preparation: 2mmol of 9, 9-dimethylfluorene and 2.2mmol of 6-bromo-1, 1-trifluorohexane-2-one were added to 5ml of dichloromethane, dissolved and stirred, then the mixture was put into an ice bath and stirred for about ten minutes, after the reactants were completely cooled, 1.77ml of TFSA was added dropwise, and after 30 minutes of ice bath, the reaction was carried out at room temperature for 6 hours. Then, the viscous solution was dropped into methanol to obtain a fibrous solid. The polymer was redissolved in chloroform and precipitated in methanol to give a fibrous polymer which was repeatedly washed with methanol and finally dried under vacuum at 60 ℃ for 24h to give PFPA-C4.
(204) PFPA-C5 preparation: 2mmol of 9, 9-dimethylfluorene and 2.2mmol of 7-bromo-1, 1-trifluoroheptan-2-one were added to 5ml of dichloromethane, dissolved and stirred, then the mixture was put into an ice bath and stirred for about ten minutes, after the reactant was completely cooled, 1.77ml of TFSA was added dropwise, and after 30 minutes of ice bath, the reaction was carried out at room temperature for 6 hours. Then, the viscous solution was dropped into methanol to obtain a fibrous solid. The polymer was redissolved in chloroform and precipitated in methanol to give a fibrous polymer which was repeatedly washed with methanol and finally dried under vacuum at 60 ℃ for 24h to give PFPA-C5.
(3) Preparation of crosslinked network anion exchange membranes
And (3) preparing the modified polybenzimidazole (PBI-C4-Pip, PBI-C6-Pip, PBI-C4-QA, PBI-C6-QA, PBI-C4-Im and PBI-C6-Im) modified by long alkyl side chain ion conduction group prepared in the step (1) and the polyaramid polymer (PTPA-C4, PTPA-C5, PFPA-C4 and PFPA-C5) into the polyaramid alkyl crosslinked modified polybenzimidazole interpenetrating network anion exchange membrane.
The preparation method comprises the following steps:
Dissolving the prepared modified polybenzimidazole (such as PBI-C4-Pip) modified by the ion conduction group containing the long alkyl side chain in dimethyl sulfoxide, and continuously adding the prepared polyaromatic alkyl polymer (such as PTPA-C4) material after fully stirring and dissolving, wherein the molar ratio of the polyaromatic alkyl polymer to the modified polybenzimidazole modified by the ion conduction group containing the long alkyl side chain is 1:1.2, stirring at 80deg.C for 3h, casting the mixture solution on a clean glass plate, oven drying at 80deg.C for 24h, removing the membrane from the glass plate, soaking in 1M KOH for 48h, and soaking in deionized water to neutrality to obtain the anion exchange membrane (such as PTPA-C4-PBI-C4-Pip) of polyarenyl crosslinked polybenzimidazole.
As shown in Table 1, the anion exchange membranes of different polyaromatic alkyl crosslinked polybenzimidazoles were prepared by replacing PBI-C4-Pip with PBI-C6-Pip, PBI-C4-QA, PBI-C6-QA, PBI-C4-Im or PBI-C6-Im, and replacing PTPA-C4 with PTPA-C5, PFPA-C4 or PFPA-C5, respectively.
TABLE 1
The properties of the corresponding film materials are shown in table 2.
Wherein, PTPA-C4-PBI-C6-Im is prepared by the following equation:
wherein, PTPA-C4-PBI-C4-Im is prepared by the following equation:
wherein, PTPA-C4-PBI-C4-Pip is prepared by the following equation:
wherein, PTPA-C4-PBI-C6-Pip is prepared by the following equation:
wherein, PTPA-C5-PBI-C4-Pip is prepared by the following equation:
The preparation equation of the PFPA-C5-PBI-C4-Pip is as follows:
Claims (9)
1. A polyarylalkyl crosslinking modified polybenzimidazole anion exchange membrane is characterized by having the following structure:
wherein x and y are positive integers greater than or equal to 1, m is 1 or 2, n is 1,2 or 3, ar is the following structure:
FG + is an incorporated ion-conducting group, including N-methylalkylpiperidinium ion, trimethylalkylammonium ion, 1-methyl-3-alkylimidazolium ion.
2. A process for preparing a polyaromatic alkyl cross-linked modified polybenzimidazole anion exchange membrane according to claim 1, comprising the steps of:
(1) Preparation of polyaromatic alkyl polymers
Adding different aryl monomers and carbonyl monomers with different chain lengths into methylene dichloride under ice water bath to dissolve and stir, dropwise adding super acid after the reactant is completely cooled, continuing to react for 2-8 hours at room temperature after ice bath for 10-60 minutes, then dropwise adding a viscous solution into a precipitator B to obtain fibrous solid, and synthesizing the polyaromatic alkyl polymer with different side chain lengths after purification, washing and drying;
(2) Preparation of crosslinked network anion exchange membranes
Dissolving modified polybenzimidazole modified by long alkyl side chain ion conduction groups and the polyaromatic alkyl polymer obtained in the step (1) in dimethyl sulfoxide to prepare casting solution, reacting at 60-80 ℃, casting the casting solution on a glass plate, drying and forming a film, soaking the film in alkali liquor for ion exchange, soaking in deionized water to be neutral, thus obtaining the anion exchange film with a cross-linked network structure,
The modified polybenzimidazole modified by the ion conduction group containing the long alkyl side chain has the structural formula:
X is a halogen atom.
3. The method for preparing a polyaryalkyl cross-linked modified polybenzimidazole anion exchange membrane according to claim 2, wherein the aryl monomer in the step (1) is para-terphenyl, biphenyl, diphenyl ether and 9, 9-dimethylfluorene, and the structural formula of the para-terphenyl, biphenyl, diphenyl ether and 9, 9-dimethylfluorene is specifically as follows:
4. The process for preparing a polyarylalkyl crosslinking modified polybenzimidazole anion exchange membrane according to claim 2, wherein the carbonyl monomer in step (1) is 6-bromo-1, 1-trifluorohexane-2-one, 7-bromo-1, 1-trifluoroheptane-2-one.
5. The process for preparing a modified polybenzimidazole anion exchange membrane according to claim 2, wherein the superacid in step (1) is trifluoroacetic acid or trifluoromethanesulfonic acid.
6. The method for preparing a modified polybenzimidazole anion exchange membrane according to claim 2, wherein the molar ratio of the polyaromatic alkyl polymer to the modified polybenzimidazole modified with long alkyl side chain ion conducting group in the step (2) is in the range of 1:0.5-6.
7. The process for producing a polyarylalkyl crosslinking modified polybenzimidazole anion exchange membrane according to claim 2, wherein the casting solution w/v in step (2) is 3 to 10%.
8. The method for preparing a polyaromatic alkyl cross-linked modified polybenzimidazole anion exchange membrane according to claim 2, wherein the alkali liquor in the step (2) is selected from lithium hydroxide solution, sodium hydroxide solution, potassium hydroxide solution, cesium hydroxide solution or barium hydroxide solution, and the concentration range is selected from 0.2mol/L to 5mol/L.
9. The use of the polyarenyl cross-linked modified polybenzimidazole anion exchange membrane of claim 1 in the fields of fuel cells, electrolyzers, water baths, and the like.
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