CN113130953B - Cross-linked polysulfone anion-exchange membrane and preparation method thereof - Google Patents
Cross-linked polysulfone anion-exchange membrane and preparation method thereof Download PDFInfo
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- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 127
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 21
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000002791 soaking Methods 0.000 claims abstract description 18
- BCMYXYHEMGPZJN-UHFFFAOYSA-N 1-chloro-2-isocyanatoethane Chemical compound ClCCN=C=O BCMYXYHEMGPZJN-UHFFFAOYSA-N 0.000 claims abstract description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- INDIALLCZKIHFF-UHFFFAOYSA-N 4-(diethylamino)phenol Chemical compound CCN(CC)C1=CC=C(O)C=C1 INDIALLCZKIHFF-UHFFFAOYSA-N 0.000 claims abstract description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000012716 precipitator Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000005580 one pot reaction Methods 0.000 claims description 7
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000005191 phase separation Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 24
- 150000002500 ions Chemical class 0.000 description 18
- 239000003513 alkali Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 9
- 239000000446 fuel Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 230000008961 swelling Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- -1 platinum metals Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000002579 anti-swelling effect Effects 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920013655 poly(bisphenol-A sulfone) Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a cross-linking type polysulfone anion-exchange membrane and a preparation method thereof, and the preparation method specifically comprises the following steps: firstly, dissolving polysulfone in N, N-dimethylacetamide, adding chloroethyl isocyanate and stannic chloride for reaction to obtain modified polysulfone with a side chain containing isocyanate groups, heating, adding dibutyltin dilaurate and 4-diethylaminophenol for reaction to obtain modified polysulfone with a side chain terminal containing tertiary amino groups, then dissolving the modified polysulfone in an organic solvent, adding a cross-linking agent, stirring, soaking, drying, demoulding to obtain a cross-linked polysulfone membrane material, finally soaking the membrane material in NaOH solution, and washing to obtain the cross-linked polysulfone anion-exchange membrane. According to the cross-linked polysulfone anion-exchange membrane, the ion conducting group is far away from the main chain of the polymer, a phase separation structure with obvious separation of a hydrophilic region and a hydrophobic region can be formed, a layer of compact cross-linked network structure is formed, and hydroxide radicals are effectively prevented from entering the interior of the membrane to be corroded.
Description
Technical Field
The invention belongs to the technical field of preparation of fuel cell anion exchange membranes, and particularly relates to a cross-linked polysulfone anion exchange membrane and a preparation method of the polysulfone anion exchange membrane.
Background
The fuel cell is an energy conversion device which directly converts chemical energy of substances into electric energy, has the advantages of high starting speed, high conversion efficiency, small environmental pollution and the like, greatly relieves the problems of shortage of fossil fuel, environmental pollution and the like, and has good development prospect. As early as the 50 s of the 20 th century, anion exchange membrane fuel cells have been used as energy supply devices on gemini and apollo airships, have the irreplaceable advantages of other fuel cells, can use non-platinum metals as catalysts, and have the advantages of high electrode reaction speed, strong carbon monoxide tolerance and the like. The Anion Exchange Membrane (AEM) which is a core component thereof plays a decisive role, and in a sense, the development of a novel anion exchange membrane fuel cell is actually the development of a high-performance anion exchange membrane. At present, the development of high-performance anion exchange membranes is faced with a great difficulty in terms of proton conductivity and dimensional stability, and in order to obtain good proton conductivity of anion exchange membranes, more ion conducting groups need to be bonded on membrane materials, but the ion conducting groups cause the reduction of the dimensional stability of the membrane materials, and some of the ion conducting groups even cause dissolution and rupture, which seriously affects the use of the membrane materials, so that the development of anion exchange membranes with better dimensional stability and alkali resistance under high proton conductivity is urgently needed. In recent years, the problems are solved by adopting methods such as acid-base compounding, inorganic doping, chemical grafting, physical blending and the like, and the problem of imbalance between ionic conductivity and dimensional stability still cannot be solved.
Disclosure of Invention
The invention aims to provide a cross-linked polysulfone anion-exchange membrane, which solves the problems of poor dimensional stability and poor alkali resistance of the traditional anion-exchange membrane under high proton conductivity.
The invention also aims to provide a preparation method of the cross-linked polysulfone anion-exchange membrane.
The technical scheme adopted by the invention is that the cross-linked polysulfone anion-exchange membrane has a structural formula as follows:
the invention adopts another technical scheme that a preparation method of a cross-linked polysulfone anion-exchange membrane is implemented according to the following steps:
step 1: preparing modified polysulfone with side chain containing isocyanate group;
step 2: preparing modified polysulfone with tertiary amino group at the tail end of a side chain;
and 3, step 3: preparing a cross-linked polysulfone membrane material;
and 4, step 4: and (3) soaking the cross-linked polysulfone membrane material obtained in the step (3) in a 1mmol/L NaOH solution for 24-30h, and washing with distilled water until the pH value of the washing solution is unchanged to obtain the cross-linked polysulfone anion-exchange membrane.
The present invention is also characterized in that,
in the step 1, the method specifically comprises the following steps: dissolving dried polysulfone in N, N-dimethylacetamide, introducing nitrogen for protection after dissolving, introducing nitrogen for 30min, dropwise adding a mixture of chloroethyl isocyanate and stannic chloride, and reacting at 50-60 ℃ for 24-30h after dropwise adding to obtain modified polysulfone with a side chain containing isocyanate groups; the mass ratio of the polysulfone to the N, N-dimethylacetamide to the chloroethyl isocyanate to the tin tetrachloride is 1: 47: 1.9: 0.58.
in the step 2, the method specifically comprises the following steps: heating the modified polysulfone with the side chain containing the isocyanate group obtained in the step 1 to 90-110 ℃, adding dibutyltin dilaurate catalyst and 4-diethylaminophenol by a one-pot method, reacting for 10-24h at 90-110 ℃ to obtain a PSF-BN mixed solution, precipitating the mixed solution by using isopropanol as a precipitating agent, washing and drying the precipitate to obtain the modified polysulfone with the side chain end containing the tertiary amino group.
The precipitator is one or more of anhydrous methanol, anhydrous ethanol and isopropanol; the volume ratio of the precipitant to the mixed liquid is 3-5: 1.
in step 3, the method specifically comprises the following steps: and (3) dissolving the modified polysulfone with the side chain terminal containing the tertiary amino group prepared in the step (2) in an organic solvent, adding a crosslinking agent 1, 4-dibromobutane after the modified polysulfone is fully dissolved, uniformly stirring, soaking for 30-36h, then putting into a drying oven for drying, after the solvent is volatilized, removing the membrane by using distilled water, and finally drying the membrane to obtain the crosslinking polysulfone membrane material.
The organic solvent is one or a mixture of N-methyl pyrrolidone and DMSO.
The invention has the beneficial effects that: the cross-linking type polysulfone anion-exchange membrane prepared by the method has novel and simple route, the ion conduction group is far away from the main chain of the polymer, a phase separation structure with obvious separation of a hydrophilic area and a hydrophobic area can be formed, meanwhile, a layer of compact cross-linked reticular structure can be formed, hydroxide radicals are effectively prevented from entering the inside of the membrane to be corroded, the prepared anion-exchange membrane keeps good dimensional stability and alkali resistance under high proton conductivity, wherein the CPSF-BN-3 film having an ion exchange capacity of 1.53mmol/g has hydroxide conductivities of 0.035S/cm and 0.083S/cm at 25 ℃ and 85 ℃, corresponding water-absorbing swellability of only 14.1% and 25.8%, the conductivity retention of the material soaked in strong alkali for 30 days reaches 83.2%, and the material can maintain good dimensional stability and alkali resistance under high conductivity, and is expected to be used in the practical application of fuel cells.
Drawings
FIG. 1 is a Fourier infrared spectrum of a CPSF-BN film made by the process of the invention;
FIG. 2 is a graph showing the change of water absorption swelling ratio of CPSF-BN membrane prepared by the method of the invention with temperature;
FIG. 3 is a graph showing the proton conductivity of the CPSF-BN membrane prepared by the method of the invention as a function of temperature;
FIG. 4 is a graph showing the change of alkali resistance with time of CPSF-BN film prepared by the method of the present invention;
FIG. 5 is a graph showing the change of the oxidation stability with time of the CPSF-BN film prepared by the method of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a cross-linking type polysulfone anion-exchange membrane with a structural formula
The invention relates to a preparation method of a cross-linked polysulfone anion-exchange membrane, which is implemented according to the following steps:
step 1: preparing modified polysulfone (SPSF) with side chain containing isocyanate group;
the method specifically comprises the following steps: dissolving dry PSF (polysulfone) in N, N-dimethylacetamide, introducing nitrogen for protection after dissolving, dropwise adding a mixture of chloroethyl isocyanate and stannic chloride after introducing the nitrogen for 30min, and reacting at 50-60 ℃ for 24-30h after dropwise adding to obtain modified polysulfone (SPSF) with a side chain containing isocyanate groups;
wherein the mass ratio of PSF, N-dimethylacetamide, chloroethyl isocyanate to tin tetrachloride is 1: 47: 1.9: 0.58;
the chemical reaction equation for preparing SPSF is shown as formula (1):
step 2: preparing modified polysulfone (PSF-QN) containing tertiary amino groups at the tail ends of side chains;
the method specifically comprises the following steps: heating the modified polysulfone (SPSF) with the side chain containing isocyanate groups obtained in the step 1 to 90-110 ℃, adding dibutyltin dilaurate catalyst and 4-diethylaminophenol by adopting a one-pot method, reacting for 10-24h at the temperature of 90-110 ℃ to obtain a mixed solution of PSF-BN, precipitating the mixed solution by using isopropanol as a precipitator, washing and drying the precipitate to obtain the modified polysulfone (PSF-QN) with the side chain end containing tertiary amino groups;
the precipitating agent is one or more of absolute methanol, absolute ethanol and isopropanol, and the volume ratio of the precipitating agent to the mixed solution is (3-5): 1;
the chemical reaction equation for preparing the modified polysulfone SPSF with the side chain terminal containing the tertiary amino group is shown as the formula (2):
and 3, step 3: preparing a cross-linked polysulfone membrane material (CPSF-QN);
the method specifically comprises the following steps: dissolving the modified polysulfone (PSF-QN) with the side chain end containing the tertiary amino group prepared in the step 2 in an organic solvent, adding a cross-linking agent 1, 4-dibromobutane after the modified polysulfone is fully dissolved, uniformly stirring, soaking for 30-36h, then putting into a drying oven for drying, removing the solvent, removing the membrane by using distilled water after the solvent is volatilized, and finally drying the membrane to obtain a cross-linked polysulfone membrane material CPSF-QN;
wherein the organic solvent is any one or a mixture of N-methylpyrrolidone and DMSO;
the chemical reaction equation for preparing the cross-linked polysulfone membrane material (CPSF-QN) is shown as the formula (3):
and 4, step 4: preparing a cross-linked polysulfone anion-exchange membrane (CPSF-BN);
the method specifically comprises the following steps: putting the cross-linked polysulfone (CPSF-QN) obtained in the step (3) into a 1mmol/L NaOH solution for soaking for 24-30h, taking out and washing with distilled water until the pH value of a washing solution is not changed to obtain a cross-linked polysulfone anion-exchange membrane (CPSF-BN), and putting the cross-linked polysulfone anion-exchange membrane (CPSF-BN) into distilled water for standby;
wherein the structural formula of the cross-linked polysulfone anion-exchange membrane (CPSF-BN) is shown as a formula (4);
the infrared spectrogram of the cross-linking type polysulfone anion-exchange membrane material CPSF-BN prepared by the method of the invention is shown in figure 1, and 1080cm in PSF chart-1，1325cm-1And 1295cm-1is-SO2Characteristic absorption peak of (E), 1245cm-1And 1015cm-1Is the antisymmetric and symmetric stretching vibration absorption peak of the aromatic ether; 1585cm-1And 1490cm-1The peak is the characteristic absorption peak of the benzene ring; in the PSF-QN diagram, at 1482cm-1，1706cm-1And 3381cm-1Has a characteristic absorption peak of 1545cm-1A new absorption peak is generated, which is caused by the coupling of the stretching vibration of the C-N bond and the bending vibration of the N-H bond; in the CPSF-BN plot, 1637cm apart from the appearance of all characteristic absorption peaks in PSF-BN-1Characteristic absorption peaks of the C-N bond of the quaternary ammonium group appear, and changes of the infrared spectrogram indicate that CPSF-BN is successfully prepared.
And (3) testing the Ion Exchange Capacity (IEC) of the successfully prepared cross-linked polysulfone anion-exchange membrane CPSF-BN (mass is m) by adopting a back titration method: placing CPSF-BN at 0.01mol/L volume is V1Soaking in dilute hydrochloric acid for 36h, titrating the mixed solution with 0.01mol/L NaOH solution by taking phenolphthalein as an indicator after the completion of the soaking, wherein the consumed volume is V2By IEC ═ C1V1-C2V2) The IEC of the anion exchange membrane was calculated as/m. According to the invention, a series of CPSF-BN membrane materials are prepared by controlling the reaction time in the step 2 and are respectively marked as CPSF-BN-1, CPSF-BN-2 and CPSF-BN-3 membranes, the IEC of the CPSF-BN membrane materials is 1.24mmol/g, 1.33mmol/g and 1.53mmol/g, and the performance change of the CPSF-BN membrane materials is researched.
The CPSF-BN membrane can conduct ion conduction only by absorbing water, and the water absorption rate is very important for the CPSF-BN membrane, the change of the water absorption rate of the CPSF-BN membrane along with the temperature is shown in figure 2 in the research of the change process of the performance of the CPSF-BN membrane along with the temperature, 3 anion exchange membranes have a large range of water absorption areas due to the fact that hydrophilic groups are far away from a main polymer chain, water and ion clusters are convenient to form, the water absorption rate of membrane materials is large, the water absorption rate of the CPSF-BN-3 membrane is increased along with the increase of IEC, the maximum water absorption rate is as high as 27.6% and 55.1%, and even higher than that of commercial Nafion115 under the same conditions (28.6% and 42.7% respectively), and the water absorption rate shows good water absorption capacity.
In the field of anion exchange membranes, high conductivity and high dimensional stability are one of the targets pursued by anion exchange membranes, and in order to obtain higher ion conductivity, higher ion conductivity groups need to be bonded, but too high bonding amount of the ion conductivity groups causes the problems of poor dimensional stability and poor alkali resistance of the anion exchange membranes, and the use of membrane materials is seriously influenced.
The change curve of the water absorption swelling rate of the CPSF-BN membrane prepared by the invention along with the temperature is shown in figure 3, because the length of the side chain is very long, the influence of a hydrophilic group far away from the main chain on the main chain is very small, so that the prepared anion exchange membrane still keeps very low water absorption swelling rate under high water absorption, and simultaneously forms a cross-linked network structure through cross-linking reaction, so that the anti-swelling rate of the CPSF-BN membrane is increased, and although the maximum water absorption rate of the CPSF-BN-3 membrane at 25 ℃ and 85 ℃ is up to 27.6 percent and 55.1 percent, the water absorption swelling rate is only 14.1 percent and 25.8 percent and is far lower than the water absorption swelling rate of a commercial Nafion115 membrane under the same condition (the swelling rate of the Nafion115 membrane is 25 percent and 55 percent), and the CPSF-BN-membrane shows excellent dimensional stability.
As the most core index of the anion exchange membrane, the hydroxide ion conductivity determines the conductivity of the anion exchange membrane, the change curve of the hydroxide ion conductivity of the CPSF-BN membrane prepared by the invention along with the temperature is shown in figure 4, the CPSF-BN membrane shows good ion conductivity which is determined by the structures of the two, because the length of a side chain is very large, the distance between an ion conducting group and a main chain is very far, an obvious microphase separation structure can be formed, an ion transmission channel is widened, and simultaneously the volumes of water and ion clusters are increased, which are beneficial to the increase of the ion conductivity. The ion conductivity of the CPSF-BN-3 membrane with the highest ion conductivity reaches 35mS/c and 83mS/cm at room temperature and 85 ℃, and the CPSF-BN-3 membrane meets the requirement of a fuel cell on the ion conductivity of the membrane material (0.01S/cm) and shows good ion conductivity.
Soaking the CPSF-BN membrane in KOH solution at the temperature of 80 ℃, controlling the soaking time, and measuring the alkali resistance of the anion exchange membrane by measuring the retention rate of hydroxyl ion conductivity of the membrane material.
The change curve of the retention value of the ionic conductivity of the 3 anion exchange membranes prepared by the invention in an alkaline environment along with time is shown in figure 5, the anion exchange membranes keep good alkali resistance, which is related to the water absorption swelling property of the anion exchange membranes, hydrophilic groups are far away from a main polymer chain, and a compact cross-linked network structure is formed at the same time, so that hydroxide radicals and free radicals can be effectively prevented from entering the membrane interior to be corroded, and the good alkali resistance is effectively kept. The CPSF-BN-1, CPSF-BN-2 and CPSF-BN-3 films are soaked in an alkaline solution for 30 days, the conductivity retention rate of hydroxide ions reaches 79.1 percent, 81.1 percent and 83.2 percent, and good alkali resistance is kept.
Example 1
The invention relates to a preparation method of a cross-linked polysulfone anion-exchange membrane, which is implemented according to the following steps:
step 1: preparing modified polysulfone (SPSF) with side chain containing isocyanate group;
the method specifically comprises the following steps: dissolving dry PSF (polysulfone) in N, N-dimethylacetamide, introducing nitrogen for protection after dissolving, dropwise adding a mixture of chloroethyl isocyanate and stannic chloride after introducing the nitrogen for 30min, and reacting at 50 ℃ for 24-30h after dropwise adding to obtain modified polysulfone (SPSF) with a side chain containing isocyanate groups;
wherein the mass ratio of PSF, N-dimethylacetamide, chloroethyl isocyanate to stannic chloride is 1: 47: 1.9: 0.58;
step 2: preparing modified polysulfone (PSF-QN) with a tertiary amino group at the tail end of a side chain;
the method specifically comprises the following steps: heating the modified polysulfone (SPSF) with the side chain containing the isocyanate group obtained in the step 1 to 90 ℃, adding dibutyltin dilaurate catalyst and 4-diethylaminophenol by adopting a one-pot method, reacting for 10 hours at 90 ℃ to obtain a PSF-QN mixed solution, precipitating the mixed solution by using isopropanol as a precipitator, washing and drying the precipitate to obtain the modified polysulfone (PSF-QN) with the side chain terminal containing the tertiary amino group;
wherein, the precipitator is absolute methanol, and the volume ratio of the precipitator to the mixed solution is 3: 1;
and 3, step 3: preparing a cross-linked polysulfone membrane material;
the method specifically comprises the following steps: dissolving the modified polysulfone (PSF-QN) with the side chain terminal containing the tertiary amino group prepared in the step 2 in an organic solvent, adding a cross-linking agent 1, 4-dibromobutane after the modified polysulfone is fully dissolved, uniformly stirring, soaking for 30 hours, then putting into a drying oven for drying, removing the solvent, removing the membrane by using distilled water after the solvent is volatilized, and finally drying the membrane to obtain a cross-linked polysulfone membrane material;
wherein the organic solvent is N-methyl pyrrolidone;
and 4, step 4: preparing a cross-linked polysulfone anion-exchange membrane (CPSF-QN);
the method specifically comprises the following steps: and (3) putting the cross-linked polysulfone membrane material (CPSF-QN) obtained in the step (3) into a 1mol/L NaOH solution for soaking for 24h, taking out the cross-linked polysulfone membrane material and washing the cross-linked polysulfone membrane material with distilled water until the pH value of the washing solution is not changed to obtain a cross-linked polysulfone anion-exchange membrane (CPSF-BN), and putting the cross-linked polysulfone anion-exchange membrane (CPSF-BN) into the distilled water for standby.
Example 2
The invention relates to a preparation method of a cross-linked polysulfone anion-exchange membrane, which is implemented according to the following steps:
step 1: preparing modified polysulfone (SPSF) with side chain containing isocyanate group;
the method specifically comprises the following steps: dissolving dry PSF (polysulfone) in N, N-dimethylacetamide, introducing nitrogen for protection after dissolving, introducing nitrogen for 30min, dropwise adding a mixture of chloroethyl isocyanate and stannic chloride, and reacting at 55 ℃ for 25h after dropwise adding to obtain modified polysulfone (SPSF) with a side chain containing isocyanate groups;
wherein the mass ratio of PSF, N-dimethylacetamide, chloroethyl isocyanate to stannic chloride is 1: 47: 1.9: 0.58;
step 2: preparing modified polysulfone (PSF-QN) with a tertiary amino group at the tail end of a side chain;
the method specifically comprises the following steps: heating the modified polysulfone (SPSF) with the side chain containing the isocyanate group obtained in the step 1 to 100 ℃, adding dibutyltin dilaurate catalyst and 4-diethylaminophenol by adopting a one-pot method, reacting for 15 hours at the temperature of 100 ℃ to obtain a mixed solution of PSF-QN, precipitating the mixed solution by using isopropanol as a precipitator, washing and drying the precipitate to obtain the modified polysulfone (PSF-QN) with the side chain end containing the tertiary amino group;
wherein the precipitator is absolute ethyl alcohol, and the volume ratio of the precipitator to the mixed solution is 4: 1;
and step 3: preparing a cross-linked polysulfone membrane material;
the method specifically comprises the following steps: dissolving the modified polysulfone (PSF-QN) with the side chain end containing the tertiary amino group prepared in the step 2 in an organic solvent, adding a cross-linking agent 1, 4-dibromobutane after the modified polysulfone is fully dissolved, uniformly stirring, soaking for 35 hours, then putting the mixture into a drying oven for drying, removing the solvent, removing the membrane by using distilled water after the solvent is volatilized, and finally drying the membrane to obtain a cross-linked polysulfone membrane material;
wherein the organic solvent is DMSO;
and 4, step 4: preparing a cross-linked polysulfone anion-exchange membrane (CPSF-BN);
the method comprises the following specific steps: and (4) soaking the cross-linked polysulfone membrane material (CPSF-QN) obtained in the step (3) in a 1mol/L NaOH solution for 28h, taking out the membrane material and washing the membrane material with distilled water until the pH value of the washing solution is not changed to obtain a cross-linked polysulfone anion exchange membrane (CPSF-BN), and putting the cross-linked polysulfone anion exchange membrane (CPSF-BN) into the distilled water for standby.
Example 3
The invention relates to a preparation method of a cross-linked polysulfone anion-exchange membrane, which is implemented according to the following steps:
step 1: preparing modified polysulfone (SPSF) with side chain containing isocyanate group;
the method specifically comprises the following steps: dissolving dry PSF (polysulfone) in N, N-dimethylacetamide, introducing nitrogen for protection after dissolving, introducing nitrogen for 30min, dropwise adding a mixture of chloroethyl isocyanate and stannic chloride, and reacting at 60 ℃ for 30h after dropwise adding to obtain modified polysulfone (SPSF) with a side chain containing isocyanate groups;
wherein the mass ratio of PSF, N-dimethylacetamide, chloroethyl isocyanate to stannic chloride is 1: 47: 1.9: 0.58;
step 2: preparing modified polysulfone (PSF-QN) with a tertiary amino group at the tail end of a side chain;
the method specifically comprises the following steps: heating the modified polysulfone (SPSF) with the side chain containing the isocyanate group obtained in the step 1 to 110 ℃, adding dibutyltin dilaurate catalyst and 4-diethylaminophenol by adopting a one-pot method, reacting for 24 hours at the temperature of 110 ℃ to obtain a mixed solution of PSF-BN, precipitating the mixed solution by using isopropanol as a precipitator, washing and drying the precipitate to obtain the modified polysulfone (PSF-QN) with the side chain end containing the tertiary amino group;
wherein the precipitator is isopropanol, and the volume ratio of the precipitator to the mixed solution is 5: 1;
and step 3: preparing a cross-linked polysulfone membrane material;
the method specifically comprises the following steps: dissolving the modified polysulfone (PSF-QN) with the side chain end containing the tertiary amino group prepared in the step 2 in an organic solvent, adding a cross-linking agent 1, 4-dibromobutane after the modified polysulfone is fully dissolved, uniformly stirring, soaking for 36h, then putting the mixture into a drying oven for drying, removing the solvent, removing the membrane by using distilled water after the solvent is volatilized, and finally drying the membrane to obtain a cross-linked polysulfone membrane material;
wherein the organic solvent is a mixture of N-methylpyrrolidone and DMSO;
and 4, step 4: preparing a cross-linked polysulfone anion-exchange membrane (CPSF-BN);
the method comprises the following specific steps: and (3) putting the cross-linked polysulfone membrane material (CPSF-BN) obtained in the step (3) into a 1mmol/L NaOH solution for soaking for 30h, taking out the cross-linked polysulfone membrane material and washing the cross-linked polysulfone membrane material with distilled water until the pH value of the washing solution is not changed to obtain the cross-linked polysulfone anion-exchange membrane (CPSF-BN), and putting the cross-linked polysulfone anion-exchange membrane (CPSF-BN) into the distilled water for standby.
According to the method, bisphenol A polysulfone is used as a base material, a simple one-pot method is adopted to introduce-NCO groups at the tail ends of polysulfone side chains, then the-NCO groups react with hydroxyl groups to introduce tertiary amino groups, and finally the polysulfone anion exchange membrane with a long hydrophilic and hydrophobic region distance and a cross-linked net structure is prepared through a cross-linking reaction, so that the problem that the traditional anion exchange membrane is poor in dimensional stability under high water absorption is solved, the anion exchange membrane can still keep good dimensional stability and alkali resistance under high proton conductivity, and the anion exchange membrane is expected to be used for the practical application of alkaline fuel cells.
Claims (3)
1. A cross-linking type polysulfone anion-exchange membrane is characterized in that the structural formula is as follows:
2. the preparation method of the cross-linked polysulfone anion-exchange membrane according to claim 1, which is implemented by the following steps:
step 1: preparing modified polysulfone with side chain containing isocyanate group; the method specifically comprises the following steps: dissolving dried polysulfone in N, N-dimethylacetamide, introducing nitrogen for protection after dissolving, introducing nitrogen for 30min, dropwise adding a mixture of chloroethyl isocyanate and stannic chloride, and reacting at 50-60 ℃ for 24-30h after dropwise adding to obtain modified polysulfone with a side chain containing isocyanate groups; the mass ratio of the polysulfone to the N, N-dimethylacetamide to the chloroethyl isocyanate to the tin tetrachloride is 1: 47: 1.9: 0.58;
step 2: preparing modified polysulfone with tertiary amino group at the tail end of a side chain; the method specifically comprises the following steps: heating the modified polysulfone with the side chain containing isocyanate groups obtained in the step 1 to 90-110 ℃, adding dibutyltin dilaurate catalyst and 4-diethylaminophenol by adopting a one-pot method, reacting for 10-24h at 90-110 ℃ to obtain a PSF-BN mixed solution, precipitating the mixed solution by using isopropanol as a precipitator, washing and drying the precipitate to obtain the modified polysulfone with the side chain end containing tertiary amino groups;
and 3, step 3: preparing a cross-linked polysulfone membrane material; the method specifically comprises the following steps: dissolving the modified polysulfone with the side chain end containing the tertiary amino group prepared in the step 2 in an organic solvent, adding a cross-linking agent 1, 4-dibromobutane after the modified polysulfone is fully dissolved, uniformly stirring, soaking for 30-36h, then putting into a drying oven for drying, after the solvent is volatilized, removing the membrane with distilled water, and finally drying the membrane to obtain a cross-linked polysulfone membrane material;
and 4, step 4: and (3) soaking the cross-linked polysulfone membrane material obtained in the step (3) in a 1mmol/L NaOH solution for 24-30h, and washing with distilled water until the pH value of the washing solution is unchanged to obtain the cross-linked polysulfone anion-exchange membrane.
3. The method for preparing a cross-linked polysulfone anion-exchange membrane according to claim 2, wherein the organic solvent is any one or a mixture of N-methylpyrrolidone and DMSO.
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