CN115286784B - Preparation method of solvent-resistant anion exchange membrane with cross-linked structure - Google Patents
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Abstract
The invention discloses a preparation method of a solvent-resistant cross-linked structure anion exchange membrane, which comprises the following steps: (1) Preparing a cross-linking agent 4- (N, N-dimethyl amine) picoline (APy); (2) Preparation of small molecule pyridinium salt by mole ratio of APy to 1-bromopropane/1-bromohexane or 3-bromo-1-propanol/6-bromo-1-hexanol 1:1 heating in a mixed mode to obtain APy-nC (n=3 and 6) or APy-nC-OH (n=3 and 6); (3) And feeding a crosslinking agent (APy) and a side chain APy-nC (n=3 and 6) or APy-nC-OH (n=3 and 6) according to a certain proportion to obtain a casting solution, pouring the casting solution on a glass plate, and drying at 60-100 ℃ to obtain the anion exchange membrane with the solvent-resistant crosslinking structure. The organic solvent anion exchange membrane prepared by the invention has low swelling rate, high organic solvent tolerance and high desalination rate.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method of a solvent-resistant anion exchange membrane with a cross-linked structure.
Background
Electrodialysis technology (ED) is used for the desalination of complex brine solutions in the food, beverage, pharmaceutical and chemical industries, biotechnology and wastewater treatment. The method has the advantages of low energy consumption, simple operation equipment and the like, and is considered as one of the most developed potential water treatment technologies. Organic wastewater is produced in many industrial and agricultural fields, for example, DMSO, a common solvent, has been widely found in wastewater of pharmaceutical, textile, membrane industries, and the like. DMF and DMAc, which have low volatility, are widely used as electrolytes and non-electrolytes in the production of fibers, paints and foils, and acetone, which is indispensable in the industries of pharmaceutical, chemical, petroleum, leather, etc., are very harmful to human bodies and the environment. For ED treatment of organic wastewater, ion Exchange Membranes (IEMs) with superior resistance to organic solvents are needed. Some conventional IEMs may undergo degradation, functional group detachment or significant swelling in organic salt solutions, all of which are detrimental to ED. Therefore, the development of IEMs with excellent resistance to organic solvents is a key issue to solving such problems.
However, reports on organic solvent resistant IEM have been limited to date. Brominated poly (2, 6-dimethyl-1, 4-phenoxy) (BPPO) has wide application in ED, gas separation, fuel cells, 3D printing, vanadium redox flow batteries and the like, and the BPPO has the advantages of high thermal stability, good dimensional stability, rich modification sites and the like. But without crosslinking, BPPO-based IEMs are unstable in corrosive nonpolar solvents. To improve solvent resistance, construction of a three-dimensional network structure is one of important strategies for improving solvent resistance of films. The IEM has strong dimensional stability and long-term organic solvent resistance, and has application prospect.
Disclosure of Invention
The invention aims to provide a preparation method of a solvent-resistant anion exchange membrane with a cross-linked structure.
In order to solve the above-mentioned purpose, the invention adopts the following technical scheme:
a preparation method of a solvent-resistant cross-linked anion exchange membrane comprises the following steps:
step (1) synthesis of 4- (N, N-dimethylamine) picoline APy: adding a certain amount of 4- (aminomethyl) pyridine, formic acid and formaldehyde into a flask with a condenser; the mixture was heated to a temperature under nitrogen for 18h under reflux, cooled to room temperature, poured into NaOH solution of a certain concentration, and then treated with dichloromethane (CH 2 Cl 2 ) Extracting; the resulting organic phase was treated with anhydrous magnesium sulfate (MgSO 4 ) Drying; finally, the brown oily product as shown in formula (I) was collected by rotary evaporation;
the chemical structures of the 4 small molecule pyridinium salts in the step (2) are shown as a formula (II), the 4 small molecule pyridinium salts are named as APy-nC and APy-nC-OH, n=3 and 6, wherein n represents methylene (-CH) 2 Number of (-); the preparation process is as follows: dissolving 1-bromopropane/1-bromohexane or 3-bromo-1-propanol/6-bromo-1-hexanol with a certain mass and 4- (N, N-dimethylamine) picoline APy prepared in the step (1) in a polar solvent, heating the mixture solution to 60 ℃ for 24 hours, cooling to room temperature after the reaction is finished, fully washing the product with THF, and then drying in a vacuum drying oven at 60 ℃ for 24 hours;
preparation of the anion exchange membrane in step (3): weighing a certain amount of brominated polyphenylene oxide BPPO shown in a formula (III), and dissolving in a polar solvent; then adding a certain amount of 4-pyridine propanol Py-3, APy-nC, n=3 and 6 or APy-nC-OH, n=3 and 6, adding a certain amount of cross-linking agent APy into the mixed solution of the APy-nC, n=3 and 6 or the APy-nC-OH, n=3 and 6 and BPPO, stirring at room temperature until the cross-linking agent APy is dissolved, casting the mixture on a clean glass plate, and vacuum drying at 60-100 ℃ for 12-36 hours to obtain 5 types of anion exchange membranes: BPPO-Py-3 having a chemical structure shown In (IV), BPPO-apt-nC, n=3 and 6 and BPPO-apt-nC-OH, n=3 and 6, and having a chemical structure shown in (V);
preferably, the reaction time in the step (1) is 12-24 hours, and the concentration of the added NaOH solution is 0.5-3.5mol L –1 Preferably 18 hours, 2.0mol L –1 。
Preferably, the heating temperature in step (2) is 30-80 ℃, and the reaction time is 12-48 hours, preferably 60 ℃, for 24 hours.
Preferably, the number n of methylene groups in step (2) is preferably 6.
Preferably, the polar solvent in the step (2) is one or more of tetrahydrofuran, N-methylpyrrolidone and N, N-dimethylformamide, preferably tetrahydrofuran.
Preferably, the polar solvent in the step (3) is N-methyl pyrrolidone.
Preferably, the reaction conditions described in step (3) are preferably 25℃for 1 to 8 hours.
Preferably, the temperature of the vacuum drying in the step (3) is preferably 80 ℃ for 24 hours.
Preferably, the brominated polyphenylene ether BPPO described in step (4) has a benzyl substitution degree of 0.55.
The beneficial effects are that:
the invention prepares a series of pyridinium side chain functionalized poly (2, 6-dimethyl-1, 4-phenyl oxide) base Anion Exchange Membranes (AEMs) for electrodialysis. The AEMs prepared have a three-dimensional network structure, and the optimized AEMs have lower membrane surface resistance and low expansion rate in water and organic solvents. The AEMs have rich ion exchange groups, can establish a proper ion channel to reduce ion transmission resistance, are favorable for desalination, and have better dimensional stability; because of the cross-linking structure, the main chains are mutually locked, the side chains are mutually entangled with the alkyl chains in the main chains, the structure is more compact, and the organic solvent resistance is stronger. It is soaked in organic solvent for a long period without obvious change in appearance. In addition, the organic solvent treated AEM remained high in desalination rate without degradation for a long time during electrodialysis desalination, indicating that the produced AEM has the ability to withstand strong polar organic solvents and is due to commercial membrane AMX. This is because the built compact three-dimensional network cross-linked structure and the hydrophobicity of the alkyl segments greatly enhance the dimensional stability and resistance to organic solvents of the produced AEM.
Drawings
FIGS. 1a to 1e are schematic views of anion exchange membranes produced in examples 1 to 5, respectively.
FIG. 2 is a graph showing the physicochemical properties of the anion exchange membranes produced in examples 1 to 5 of the present invention, respectively.
FIGS. 3a and 3b are graphs showing the water absorption and swelling ratios of the anion exchange membranes prepared in examples 1 to 5 of the present invention, respectively, in water and DMSO.
FIG. 4 is a graph showing a comparison of anion exchange membranes prepared in examples 1 to 5 of the present invention before and after soaking in 60% acetone, 60% DMSO, 60% DMF and 60% DMAc solution for 90 days.
FIG. 5 is a graph showing the resistance of the anion exchange membranes prepared in examples 1-5 of the present invention after 1 day immersion in 60% acetone, 60% DMSO, 60% DMF and 60% DMAc solution.
FIGS. 6 a-6 d are graphs comparing the electrodialysis desalination test performed for 210 minutes after immersing the anion exchange membranes prepared in examples 1-5 of the present invention in 0% DMSO, 20% DMSO, and 60% DMSO for 1 day, and comparing with commercial membrane AMX.
FIGS. 7a to 7c, 7d to 7f and 7g to 7i are respectively graphs of energy consumption and current efficiency, current-voltage curves and water migration during electrodialysis of the anion-exchange membrane ions prepared in examples 1 to 5 of the present invention.
FIGS. 8a to 8d and 8e show the stability of the organic resistance for a long period of time of example 6, which was carried out by preparing an anion exchange membrane according to example 3 of the present invention, and FIG. 8f shows the dynamic electrodialysis of example 7, which was carried out by preparing an anion exchange membrane according to example 3 of the present invention.
Detailed Description
For further explanation of the technical solution of the present invention, preferred embodiments of the present invention are described below with reference to specific examples, but it should be understood that these descriptions are only for further explanation of features and advantages of the present invention, and are not limiting of the claims of the present invention.
Example 1:
synthesis of 4- (N, N-dimethylamine) picoline (APy): into a 50mL three-necked round bottom flask equipped with a condenser were charged 4.33 g of 4- (aminomethyl) pyridine, 9.21 g of formic acid and 3.68 g of formaldehyde. The mixture is put under N 2 Heating to 60 ℃ and refluxing for 18h, cooling to room temperature, and then mixing according to the following ratio of 1:3 proportion is poured into 2.0 mol.L –1 The excess acid was treated to neutrality in NaOH solution and then treated with dichloromethane (CH 2 Cl 2 ) And (5) extracting. The resulting organic phase was treated with anhydrous magnesium sulfate (MgSO 4 ) And (5) drying. Finally, 4.10 g of the product 4- (N, N-dimethylamine) picoline (APy) was collected as a dark brown oil by rotary evaporation.
Preparation of side chain type pyridinium functionalized brominated polyphenylene oxide BPPO-Py-3 anion exchange membrane: 1.0 g of BPPO and 0.34 g of 4-pyridinepropanol were weighed into 30mL of NMP, respectively, in a flask, and stirred at room temperature until dissolved, to obtain a casting solution. The casting solution thus prepared was poured onto a clean glass plate having an effective size of 8cm X8 cm (width X length), dried under vacuum at 80℃for 24 hours, and the residual solvent was removed to obtain a colored thin film BPPO-Py-3 having a film thickness of 85. Mu.m.
Performance of BPPO-Py-3 anion exchange membrane: the parameters of the prepared brominated polyphenylene oxide-based anion exchange membrane, such as ion exchange capacity, membrane surface resistance, water absorption and swelling ratio, ion migration number, organic solvent desalination resistance and the like are shown in fig. 2, 3a, 3b, 5, 6 a-6 d, 7 a-7 c, 7 d-7 f and 7 g-7 i. Here, the prepared anion exchange membrane was mainly used as a comparative test. (for specific test methods, see literature report: journal of Membrane Science 574 (2019) 181-195;Journal of Membrane Science 577 (2019) 153-164). In addition, the prepared anion exchange membrane is subjected to specific organic solvents (acetone, DMAc, DMSO and DMF) and then is subjected to a membrane surface resistance test, and the organic solvent resistance of AEMs is primarily evaluated. The AEM samples were further soaked in 0% DMSO (deionized water), 20% DMSO, 60% DMSO solution (mixture of water and DMSO) for 24h and ED seawater desalination experiments were performed in a self-made ED device, with the results shown in figures 6 a-6 d.
Example 2:
the procedure for the preparation of 4- (N, N-dimethylamine) picoline (APy) was as in example 1.
Synthesis of APy-3C: 2.46 g of 1-bromopropane (0.02 mmol) and 2.72 g (0.02 mmol) of 4- (N, N-dimethylamine) picoline APy were weighed, dissolved in 50mL of tetrahydrofuran, heated to 60℃and maintained for 24 hours. The resulting product was washed with tetrahydrofuran several times to give 3.42 g of APy-3C.
Preparation of side-chain pyridine salt functionalized brominated polyphenylene oxide BPPO-APy-3C anion exchange membrane 1.0 g of BPPO, 0.54 g of APy-3C and 0.29 g of APy are respectively weighed, 30mL of NMP is added into a flask, and stirred at room temperature until the solution is dissolved to obtain casting solution. The casting solution thus prepared was poured onto a clean glass plate having an effective size of 8cm X8 cm (width X length), dried under vacuum at 80℃for 24 hours, and the residual solvent was removed to obtain a colored thin film BPPO-APy-3C having a film thickness of 85. Mu.m.
The performance of the BPPO-APy-3C anion exchange membrane was tested and the method was the same as in example 1.
Example 3:
the procedure for the preparation of 4- (N, N-dimethylamine) picoline (APy) was as in example 1.
Synthesis of APy-6C: 3.30 g of 1-bromohexane (0.02 mmol) and 2.72 g (0.02 mmol) of 4- (N, N-dimethylamine) picoline APy were weighed, dissolved in 50mL of tetrahydrofuran, heated to 60℃and maintained for 24 hours. The resulting product was washed with tetrahydrofuran several times to give 3.91 g of APy-6C.
Preparation of side-chain pyridine salt functionalized brominated polyphenylene oxide BPPO-APy-6C anion exchange membrane 1.0 g of BPPO, 0.66 g of APy-6C and 0.29 g of APy are respectively weighed, 30mL of NMP is added into a flask, and stirred at room temperature until the solution is dissolved to obtain casting solution. The casting solution thus prepared was poured onto a clean glass plate having an effective size of 8cm X8 cm (width X length), dried under vacuum at 80℃for 24 hours, and the residual solvent was removed to obtain a colored thin film BPPO-APy-6C having a film thickness of 85. Mu.m.
The performance of the BPPO-APy-6C anion exchange membrane was tested and the method was the same as in example 1.
Example 4:
the procedure for the preparation of 4- (N, N-dimethylamine) picoline (APy) was as in example 1.
Synthesis of APy-3C-OH: 2.78 g of 3-bromo-1-propanol (0.02 mmol) and 2.72 g (0.02 mmol) of 4- (N, N-dimethylamine) picoline APy were weighed out, dissolved in 50mL of tetrahydrofuran, heated to 60℃and maintained for 24 hours. The resulting product was washed with tetrahydrofuran a number of times to give 3.57 g of APy-3C-OH.
The preparation of side chain type pyridine salt functionalized brominated polyphenylene oxide BPPO-APy-3C-OH anion exchange membrane comprises the steps of respectively weighing 1.0 g of BPPO, 0.60 g of APy-3C-OH and 0.29 g of APy, adding 30mL of NMP into a flask, and stirring at room temperature until the solution is dissolved to obtain casting solution. The casting solution thus prepared was poured onto a clean glass plate having an effective size of 8cm X8 cm (width X length), dried under vacuum at 80℃for 24 hours, and the residual solvent was removed to obtain a colored thin film BPPO-APy-3C-OH having a film thickness of 90. Mu.m.
The performance of the BPPO-APy-3C-OH anion exchange membrane was tested and the method was the same as in example 1.
Example 5:
the procedure for the preparation of 4- (N, N-dimethylamine) picoline (APy) was as in example 1.
Synthesis of APy-6C-OH: 3.62 g of 3-bromo-1-propanol (0.02 mmol) and 2.72 g (0.02 mmol) of 4- (N, N-dimethylamine) picoline APy were weighed, dissolved in 50mL of tetrahydrofuran, heated to 60℃and maintained for 24 hours. The resulting product was washed with tetrahydrofuran a number of times to give 3.57 g of APy-6C-OH.
The preparation of side chain type pyridine salt functionalized brominated polyphenylene oxide BPPO-APy-6C-OH anion exchange membrane comprises the steps of respectively weighing 1.0 g of BPPO, 0.70 g of APy-6C-OH and 0.29 g of APy, adding 30mL of NMP into a flask, and stirring at room temperature until the solution is dissolved to obtain casting solution. The casting solution thus prepared was poured onto a clean glass plate having an effective size of 8cm X8 cm (width X length), dried under vacuum at 80℃for 24 hours, and the residual solvent was removed to obtain a colored thin film BPPO-APy-6C-OH having a film thickness of 95. Mu.m.
The performance of the BPPO-APy-6C-OH anion exchange membrane was tested and the method was the same as in example 1.
Example 6:
the BPPO-APy-6C anion-exchange membrane prepared in example 3 was subjected to a long-term organic solvent-resistant desalting stability test. BPPO-APY-6C AEM was first soaked in 20% DMSO (80% water) solution for 1 day, then subjected to a desalting test in an electrodialysis unit for 90 minutes for a total of 15 cycles. After repeating the test 15 times, the same BPPO-APY-6C AEM was immersed in a 20% DMSO (80% water) solution and removed on days 3, 8 and 20, and subjected to electrodialysis desalination test for 90 minutes for 5 cycles, and the results are shown in FIGS. 8 a-8 d and 8 e.
Example 7:
a simulated dynamic electrodialysis desalination experiment was performed on the BPPO-APy-6C anion exchange membrane prepared in example 3, and a mixed solution of 0.5M NaCl in 20% DMSO (80% water) was added as a feed solution in a concentration chamber (DC) and a desalination chamber (CC) for testing. Collecting solution samples from DC and CC at prescribed times, performing Cl - Titration to determine Cl - Concentration. A comparative test was also performed with a 0.5M NaCl aqueous solution as shown in FIG. 8 f.
Claims (8)
1. A preparation method of a solvent-resistant cross-linked anion exchange membrane comprises the following steps:
step (1) synthesis of 4- (N, N-dimethylamine) picoline APy: adding a certain amount of 4- (aminomethyl) pyridine, formic acid and formaldehyde into a flask with a condenser; the mixture was heated to a temperature under nitrogen for 18h under reflux, cooled to room temperature, poured into NaOH solution of a certain concentration, and then treated with dichloromethane (CH 2 Cl 2 ) Extracting; the resulting organic phase was treated with anhydrous magnesium sulfate (MgSO 4 ) Drying; finally, the brown oily product as shown in formula (I) was collected by rotary evaporation;
the chemical structures of the 4 small molecule pyridinium salts in the step (2) are shown as a formula (II), the 4 small molecule pyridinium salts are named as APy-nC and APy-nC-OH, n=3 and 6, wherein n represents methylene (-CH) 2 Number of (-); the preparation process is as follows: dissolving 1-bromopropane/1-bromohexane or 3-bromo-1-propanol/6-bromo-1-hexanol and 4- (N, N-dimethyl amine) picoline APy prepared in step (1) in polar solvent, heating the mixture solution to 60 ℃ for 24 hours, cooling to room temperature after the reaction is finished, and fully washing the product with THFDrying in a vacuum drying oven at 60 ℃ for 24 hours;
preparation of the anion exchange membrane in step (3): weighing a certain amount of brominated polyphenylene oxide BPPO shown in a formula (III), and dissolving in a polar solvent; then adding a certain amount of ape-nC, n=3 and 6 or ape-nC-OH, n=3 and 6, adding a certain amount of cross-linking agent ape into the mixed solution of ape-nC, n=3 and 6 or ape-nC-OH, n=3 and 6 and BPPO, stirring at room temperature until the cross-linking agent ape is dissolved, casting the mixture on a clean glass plate, and vacuum drying at 60-100 ℃ for 12-36h to obtain a 4-class anion exchange membrane: BPPO-apt-nC, n=3 and 6 and BPPO-apt-nC-OH, n=3 and 6, the chemical structures of which are shown in (V);
2. the method for preparing the solvent-resistant cross-linked structured anion exchange membrane according to claim 1, wherein: the reaction time in the step (1) is 12-24 hours, and the concentration of the added NaOH solution is 0.5-3.5mol L –1 。
3. The method for preparing the solvent-resistant cross-linked structured anion exchange membrane according to claim 1, wherein: the number n of the methylene groups in the step (2) is 6.
4. The method for preparing the solvent-resistant cross-linked structured anion exchange membrane according to claim 1, wherein: the polar solvent in the step (2) is one or more of tetrahydrofuran, N-methyl pyrrolidone and N, N-dimethylformamide.
5. The method for preparing the solvent-resistant cross-linked structured anion exchange membrane according to claim 1, wherein: the polar solvent in the step (3) is N-methyl pyrrolidone.
6. The method for preparing the solvent-resistant cross-linked structured anion exchange membrane according to claim 1, wherein: the reaction condition in the step (3) is 25 ℃ and 1-8h.
7. The method for preparing the solvent-resistant cross-linked structured anion exchange membrane according to claim 1, wherein: the temperature of the vacuum drying in the step (3) is 80 o And C, the time is 24h.
8. The method for preparing the solvent-resistant cross-linked structured anion exchange membrane according to claim 1, wherein: the benzyl substitution degree of the brominated polyphenylene ether BPPO described in the step (4) is 0.55.
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