CN102050911A - Polymer anion exchange membrane and preparation method thereof - Google Patents
Polymer anion exchange membrane and preparation method thereof Download PDFInfo
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 62
- 229920000642 polymer Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002608 ionic liquid Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- 150000002500 ions Chemical class 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 7
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000003431 cross linking reagent Substances 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 20
- 238000005342 ion exchange Methods 0.000 description 13
- 150000001450 anions Chemical class 0.000 description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 2
- 238000007265 chloromethylation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
Description
技术领域technical field
本发明涉及一种聚合物阴离子交换膜及其制备方法,具体涉及一种可用于碱性燃料电池的阴离子交换膜及其制备方法。The invention relates to a polymer anion exchange membrane and a preparation method thereof, in particular to an anion exchange membrane which can be used in an alkaline fuel cell and a preparation method thereof.
背景技术Background technique
阴离子交换膜已经广泛应用于水处理,湿法冶金,化学分离以及碱性燃料电池等工业领域。传统的季铵盐型聚合物阴离子交换膜的制备方法在引入离子交换基团时都要经过氯甲基化的过程,而氯甲基化过程中要使用剧毒致癌物质氯甲醚,并且在制备阴离子交换膜的过程中用到有机溶剂,这对环境保护和人类健康都有重大危害。Anion exchange membranes have been widely used in industrial fields such as water treatment, hydrometallurgy, chemical separation and alkaline fuel cells. The traditional preparation method of quaternary ammonium salt type polymer anion exchange membrane must go through the process of chloromethylation when introducing ion exchange groups, and the highly toxic carcinogen chloromethyl ether is used in the chloromethylation process, and in Organic solvents are used in the process of preparing anion exchange membranes, which have great harm to environmental protection and human health.
申请号为201010185161.4的中国发明申请公开说明书公开了一种基于离子液体的阴离子交换膜的制备方法,是在反应器中加入咪唑类离子液体,丙烯酸酯类单体,溶剂,引发剂在惰性气体保护下45~80℃聚合5~30h,再将聚合物溶解在有机溶剂中配制成聚合物溶液,通过相转化法成膜。上述方法在聚合、成膜过程中都有溶剂的使用,溶剂的使用使得阴离子交换膜的制备过程复杂,生产成本增加,同时对环境也造成一定的污染,另外,在基体材料的选择以及在阴离子交换处理工艺上导致阴离子交换膜的离子交换容量偏低。因此人们一直在寻找过程简单、环境友好、生产成本低并且性能良好的的阴离子交换膜制备方法。The Chinese invention application publication with the application number of 201010185161.4 discloses a preparation method of anion exchange membrane based on ionic liquid, which is to add imidazole ionic liquid, acrylate monomer, solvent and initiator in the reactor under the protection of inert gas. Polymerize at 45-80°C for 5-30 hours, then dissolve the polymer in an organic solvent to prepare a polymer solution, and form a film by phase inversion. The above-mentioned methods all have the use of solvent in the process of polymerization and film formation. The use of solvent makes the preparation process of anion exchange membrane complicated, increases the production cost, and also causes certain pollution to the environment. In addition, in the selection of matrix material and in the anion The ion exchange capacity of the anion exchange membrane is low due to the exchange treatment process. Therefore, people have been looking for an anion exchange membrane preparation method with simple process, environmental friendliness, low production cost and good performance.
优良的碱性燃料电池用聚合物阴离子交换膜除了具备较高的离子电导率,良好的热稳定性和化学稳定性之外,还要有良好的机械性能和耐碱性。然而,传统的季铵盐型聚合物阴离子交换膜热稳定性和化学稳定性较差。季铵基团在碱性溶液中稳定性差,使得阴离子交换膜的性能大大下降。上述发明申请公开说明书也没有公开机械性能方面相关的数据。Excellent polymer anion exchange membranes for alkaline fuel cells not only have high ionic conductivity, good thermal and chemical stability, but also good mechanical properties and alkali resistance. However, the traditional quaternary ammonium salt type polymer anion exchange membrane has poor thermal and chemical stability. Quaternary ammonium groups have poor stability in alkaline solutions, which greatly reduces the performance of anion exchange membranes. The above-mentioned published description of the invention application also does not disclose data related to mechanical properties.
因此需要开发一种能用于碱性燃料电池的聚合物阴离子交换膜材料。Therefore, it is necessary to develop a polymer anion exchange membrane material that can be used in alkaline fuel cells.
发明内容Contents of the invention
本发明目的是提供一种聚合物阴离子交换膜及其制备方法,通过经济、简单、环境友好的制备方法制得一种具备较高的离子电导率、良好的热稳定性和化学稳定性、良好的机械性能和耐碱性的聚合物阴离子交换膜。The purpose of the present invention is to provide a polymer anion exchange membrane and its preparation method, through an economical, simple and environmentally friendly preparation method to obtain a membrane with high ion conductivity, good thermal stability and chemical stability, good Excellent mechanical properties and alkali resistance of polymeric anion exchange membranes.
为达到上述目的,本发明采用的技术方案是:一种碱性阴离子交换膜的制备方法,包括以下步骤:In order to achieve the above object, the technical scheme adopted in the present invention is: a kind of preparation method of alkaline anion exchange membrane, comprises the following steps:
1、将聚合物单体和聚合型离子液体以摩尔比为1∶2~1∶9的比例混合,再加入交联剂和引发剂,将混合液超声混合均匀,进行原位聚合制备聚合物阴离子交换膜;1. Mix the polymer monomer and the polymeric ionic liquid at a molar ratio of 1:2 to 1:9, then add a crosslinking agent and an initiator, mix the mixed solution uniformly by ultrasonic, and perform in-situ polymerization to prepare a polymer anion exchange membrane;
所述单体选自丙烯腈、苯乙烯、α-甲基苯乙烯、α-甲基丙烯腈中的一种或几种;The monomer is selected from one or more of acrylonitrile, styrene, α-methylstyrene, and α-methacrylonitrile;
所述聚合型离子液体选自:The polymeric ionic liquid is selected from:
中的一种,其中m=0~10,p=0~6,X选自:I、Br或Cl中的一种; One of, wherein m=0~10, p=0~6, X is selected from: one of I, Br or Cl;
2、将制备的阴离子交换膜浸泡在50~80℃的碱液中进行阴离子交换;其中,所述离子液体为聚合型芳杂环结构的离子液体;所述碱液为1-10M氢氧化钾或氢氧化钠的水溶液;2. Soak the prepared anion exchange membrane in alkali solution at 50-80°C for anion exchange; wherein, the ionic liquid is an ionic liquid with polymeric aromatic heterocyclic structure; the lye is 1-10M potassium hydroxide or an aqueous solution of sodium hydroxide;
上述技术方案中,所述交联剂选自:二乙烯基苯,所述交联剂质量为聚合物单体和聚合型离子液体质量之和的2%~12%。In the above technical solution, the crosslinking agent is selected from divinylbenzene, and the mass of the crosslinking agent is 2% to 12% of the sum of the mass of the polymer monomer and the polymeric ionic liquid.
上述技术方案中,所述引发剂选自:安息香乙醚、偶氮二异丁腈、中的一种;所述引发剂质量为聚合物单体和聚合型离子液体质量之和的1%~6%。In the above technical scheme, the initiator is selected from: benzoin ether, azobisisobutyronitrile, One of them; the mass of the initiator is 1% to 6% of the sum of the mass of the polymer monomer and the polymeric ionic liquid.
上述技术方案中,所述聚合反应的引发方式为加热、紫外光照或者γ射线引发。In the above technical solution, the polymerization reaction is initiated by heating, ultraviolet light or gamma rays.
本发明同时要求保护上述方法制备得到的基于离子液体的聚合物阴离子交换膜,所述阴离子交换膜可以应用在碱性燃料电池领域。The present invention also claims to protect the ionic liquid-based polymer anion exchange membrane prepared by the above method, and the anion exchange membrane can be applied in the field of alkaline fuel cells.
由于上述技术方案运用,本发明与现有技术相比具有下列优点:Due to the use of the above-mentioned technical solutions, the present invention has the following advantages compared with the prior art:
1、由于本发明采用了原位合成法,并且避免了传统的聚合物阴离子交换膜制备过程中氯甲醚的使用,同时避免了溶液浇铸成膜法制备阴离子交换膜过程中有机溶剂的使,因此方法简单,且更加经济,更加环境友好;1, because the present invention has adopted the in-situ synthesis method, and has avoided the use of chloromethyl ether in the preparation process of traditional polymer anion exchange membrane, has avoided the use of organic solvent in the anion exchange membrane process of solution casting film formation method simultaneously, Therefore, the method is simple, more economical, and more environmentally friendly;
2、本发明所得OH-型阴离子交换膜离子交换容量可达1.52mmol/g,室温下离子传导率可达3.60×10-2S·cm-1,90℃下离子传导率可达7.53×10-2S·cm-1,抗张强度可达13.53Mpa,杨氏模量可达1271Mpa,断裂伸长率可达55.34%;相对于现有技术中报道的阴离子交换膜相比,在保证了较高的离子传导率、良好的耐碱性能、良好的热稳定性用和化学稳定性的同时,更获得了良好机械性能。2. The ion exchange capacity of the OH-type anion exchange membrane obtained in the present invention can reach 1.52mmol/g, the ion conductivity can reach 3.60×10 -2 S·cm -1 at room temperature, and the ion conductivity can reach 7.53×10 -2 S·cm -1 , the tensile strength can reach 13.53Mpa, the Young's modulus can reach 1271Mpa, and the elongation at break can reach 55.34%. It has high ionic conductivity, good alkali resistance, good thermal stability and chemical stability, and also has good mechanical properties.
附图说明Description of drawings
图1为实施例十一中阴离子交换膜在60℃下1M KOH溶液中浸泡不同时间电导率随温度变化图。Fig. 1 is the change diagram of conductivity with temperature of anion exchange membrane soaked in 1M KOH solution at 60°C for different time in Example 11.
具体实施方式Detailed ways
下面结合附图及实施例对本发明作进一步描述:The present invention will be further described below in conjunction with accompanying drawing and embodiment:
实施例一:Embodiment one:
0.20g(0.85mmol),苯乙烯0.10g(0.96mmol),丙烯腈0.20g(3.73mmol),安息香乙醚0.01g,二乙烯基苯0.02g,将溶液混合均匀,涂到模具上,紫外光照(波长240nm-380nm)30min,原位聚合成膜。然后将该阴离子交换膜浸泡在50℃1M KOH溶液中24小时,将阴离子转换成OH-,本实施例获得的OH-型阴离子交换膜离子交换容量为1.47mmol/g,室温下离子传导率为3.13×10-2S·cm-1,90℃下离子传导率为6.53×10-2S·cm-1。抗张强度为11.41Mpa,杨氏模量为439.9Mpa,断裂伸长率为52.65%。 0.20g (0.85mmol), 0.10g (0.96mmol) of styrene, 0.20g (3.73mmol) of acrylonitrile, 0.01g of benzoin ethyl ether, 0.02g of divinylbenzene, mix the solution evenly, apply it on the mold, and irradiate with ultraviolet light ( Wavelength 240nm-380nm) 30min, in-situ polymerization to form a film. Then soak the anion exchange membrane in 1M KOH solution at 50°C for 24 hours to convert the anions into OH - . The ion exchange capacity of the OH - type anion exchange membrane obtained in this example is 1.47mmol/g, and the ion conductivity at room temperature is 3.13×10 -2 S·cm -1 , and the ion conductivity at 90°C is 6.53×10 -2 S·cm -1 . The tensile strength is 11.41Mpa, the Young's modulus is 439.9Mpa, and the elongation at break is 52.65%.
实施例二:Embodiment two:
0.20g(0.85mmol),丙烯腈0.30g(5.60mmol),安息香乙醚0.01g,二乙烯基苯0.02g,将溶液混合均匀,涂到模具上,紫外光照(波长240nm-380nm)30min,原位聚合成膜。然后将该阴离子交换膜浸泡在60℃5MKOH溶液中24小时,将阴离子转换成OH-,本实施例获得的OH-型阴离子交换膜离子交换容量为1.52mmol/g,室温下离子传导率为3.60×10-2S·cm-1,90℃下离子传导率为7.53×10-2S·cm-1。抗张强度为10.23Mpa,杨氏模量为521.34Mpa,断裂伸长率为55.34%。 0.20g (0.85mmol), 0.30g (5.60mmol) of acrylonitrile, 0.01g of benzoin ethyl ether, 0.02g of divinylbenzene, mix the solution evenly, apply it on the mold, irradiate with ultraviolet light (wavelength 240nm-380nm) for 30min, in situ Polymerize into film. Then soak the anion exchange membrane in 5M KOH solution at 60°C for 24 hours to convert the anions into OH - . The ion exchange capacity of the OH - type anion exchange membrane obtained in this example is 1.52 mmol/g, and the ion conductivity at room temperature is 3.60 ×10 -2 S·cm -1 , and the ion conductivity at 90°C is 7.53×10 -2 S·cm -1 . The tensile strength is 10.23Mpa, the Young's modulus is 521.34Mpa, and the elongation at break is 55.34%.
实施例三:Embodiment three:
0.20g(0.87mmol),丙烯腈0.30g(5.60mmol),安息香乙醚0.01g,偶氮二异丁腈0.02g,将溶液混合均匀,涂到模具上,75℃下聚合6个小时,原位聚合成膜。然后将该阴离子交换膜浸泡在60℃ 10M KOH溶液中将阴离子转换成OH-,本实施例获得的OH-型阴离子交换膜离子交换容量为1.53mmol/g,室温下离子传导率为3.6×10-2S·cm-1,90℃下离子传导率为6.26×10-2S·cm-1。抗张强度为10.23Mpa,杨氏模量为521.34Mpa,断裂伸长率为55.34%。 0.20g (0.87mmol), 0.30g (5.60mmol) of acrylonitrile, 0.01g of benzoin ethyl ether, 0.02g of azobisisobutyronitrile, mix the solution evenly, apply it on the mold, polymerize at 75°C for 6 hours, and in situ Polymerize into film. Then soak the anion exchange membrane in 60°C 10M KOH solution to convert anions into OH - . The ion exchange capacity of the OH - type anion exchange membrane obtained in this example is 1.53mmol/g, and the ion conductivity at room temperature is 3.6×10 -2 S·cm -1 , the ion conductivity at 90°C is 6.26×10 -2 S·cm -1 . The tensile strength is 10.23Mpa, the Young's modulus is 521.34Mpa, and the elongation at break is 55.34%.
实施例四:Embodiment four:
0.20g(0.53mmol),α-甲基丙烯腈0.2g(2.96mmol),丙烯腈0.10g(1.87mmol),安息香乙醚0.01g,二乙烯基苯0.02g,将溶液混合均匀,涂到模具上,γ射线照射10s,原位聚合成膜。然后将该阴离子交换膜浸泡在80℃3M KOH溶液中将阴离子转换成OH-,本实施例获得的OH-型阴离子交换膜离子交换容量为0.96mmol/g,室温下离子传导率为1.9×10-2S·cm-1,90℃下离子传导率为4.53×10-2S·cm-1。抗张强度为13.53Mpa,杨氏模量为671.87Mpa,断裂伸长率为35.24%。 0.20g (0.53mmol), 0.2g (2.96mmol) of α-methacrylonitrile, 0.10g (1.87mmol) of acrylonitrile, 0.01g of benzoin ether, 0.02g of divinylbenzene, mix the solution evenly, and apply it on the mold , γ-ray irradiation for 10s, in situ polymerization film. Then soak the anion exchange membrane in 3M KOH solution at 80°C to convert anions into OH - . The ion exchange capacity of the OH - type anion exchange membrane obtained in this example is 0.96 mmol/g, and the ion conductivity at room temperature is 1.9×10 -2 S·cm -1 , the ion conductivity at 90°C is 4.53×10 -2 S·cm -1 . The tensile strength is 13.53Mpa, the Young's modulus is 671.87Mpa, and the elongation at break is 35.24%.
实施例五:Embodiment five:
0.20g(0.60mmol),α-甲基丙烯腈0.10g(1.48mmol),α-甲基苯乙烯0.1g(0.85mmol),丙烯腈0.10g(1.87mmol),安息香乙醚0.01g,二乙烯基苯0.05g,将溶液混合均匀,涂到模具上,紫外光照(波长240nm-380nm)30min,原位聚合成膜。然后将该阴离子交换膜浸泡在60℃7M NaOH溶液中,将阴离子转换成OH-,本实施例获得的OH-型阴离子交换膜离子交换容量为1.12mmol/g室温下离子传导率为2.74×10-2S·cm-1,90℃下离子传导率为5.13×10-2S·cm-1。抗张强度为23.53Mpa,杨氏模量为1271Mpa,断裂伸长率为11.12%。 0.20g (0.60mmol), α-methacrylonitrile 0.10g (1.48mmol), α-methylstyrene 0.1g (0.85mmol), acrylonitrile 0.10g (1.87mmol), benzoin ethyl ether 0.01g, divinyl Benzene 0.05g, mix the solution evenly, apply it on the mold, irradiate with ultraviolet light (wavelength 240nm-380nm) for 30min, and polymerize in situ to form a film. Then soak the anion exchange membrane in 7M NaOH solution at 60°C to convert the anions into OH - . The ion exchange capacity of the OH - type anion exchange membrane obtained in this example is 1.12 mmol/g and the ion conductivity at room temperature is 2.74×10 -2 S·cm -1 , the ion conductivity at 90°C is 5.13×10 -2 S·cm -1 . The tensile strength is 23.53Mpa, the Young's modulus is 1271Mpa, and the elongation at break is 11.12%.
实施例六Embodiment six
0.25g(0.76mmol),丙烯腈0.15g(2.80mmol),0.01g,二乙烯基苯0.03g,,将溶液混合均匀,涂到模具上,紫外光照(波长240nm-380nm)30min,原位聚合成膜。然后将该阴离子交换膜浸泡在60℃1M KOH溶液中,将阴离子转换成OH-,本实施例获得的OH-型阴离子交换膜离子交换容量为1.62mmol/g,室温下离子传导率为3.53×10-2S·cm-1,90℃下离子传导率为6.11×10-2S·cm-1。抗张强度为11.26Mpa,杨氏模量为571Mpa,断裂伸长率为26.32%。 0.25g (0.76mmol), acrylonitrile 0.15g (2.80mmol), 0.01g, 0.03g of divinylbenzene, mix the solution evenly, apply it on the mold, irradiate with ultraviolet light (wavelength 240nm-380nm) for 30min, and polymerize in situ to form a film. Then soak the anion exchange membrane in 60℃ 1M KOH solution to convert anions into OH - . The ion exchange capacity of the OH - type anion exchange membrane obtained in this example is 1.62mmol/g, and the ion conductivity at room temperature is 3.53× 10 -2 S·cm -1 , and the ion conductivity at 90°C is 6.11×10 -2 S·cm -1 . The tensile strength is 11.26Mpa, the Young's modulus is 571Mpa, and the elongation at break is 26.32%.
实施例七Embodiment seven
0.20g(0.85mmol),苯乙烯0.10g(0.96mmol),丙烯腈0.2g(3.73mmol),0.01g,二乙烯基苯0.02g,将溶液混合均匀,涂到模具上,紫外光照(波长240nm-380nm)30min,原位聚合成膜。然后将该阴离子交换膜浸泡在60℃6M KOH溶液中24小时,将阴离子转换成OH-,本实施例获得的OH-型阴离子交换膜离子交换容量为1.48mmol/g室温下离子传导率为3.21×10-2S·cm-1,90℃下离子传导率为6.46×10-2S·cm-1。抗张强度为11.92Mpa,杨氏模量为433.7Mpa,断裂伸长率为48.65%。 0.20g (0.85mmol), styrene 0.10g (0.96mmol), acrylonitrile 0.2g (3.73mmol), 0.01g, 0.02g of divinylbenzene, mix the solution evenly, apply it on the mold, irradiate with ultraviolet light (wavelength 240nm-380nm) for 30min, and polymerize in situ to form a film. Then soak the anion exchange membrane in 6M KOH solution at 60°C for 24 hours to convert the anions into OH - . The ion exchange capacity of the OH - type anion exchange membrane obtained in this example is 1.48mmol/g. ×10 -2 S·cm -1 , and the ion conductivity at 90°C is 6.46×10 -2 S·cm -1 . The tensile strength is 11.92Mpa, the Young's modulus is 433.7Mpa, and the elongation at break is 48.65%.
实施例八Embodiment eight
0.20g(0.71mmol),苯乙烯0.10g(0.96mmol),丙烯腈0.20g(3.73mmol),0.01g,二乙烯基苯0.02g,将溶液混合均匀,涂到模具上,紫外光照(波长240nm-380nm)30min,原位聚合成膜。然后将该阴离子交换膜浸泡在60℃1M KOH溶液中24小时,将阴离子转换成OH-,本实施例获得的OH-型阴离子交换膜离子交换容量为1.39mmol/g,室温下离子传导率为2.75×10-2S·cm-1,90℃下离子传导率为5.16×10-2S·cm-1。抗张强度为8.98Mpa,杨氏模量为621Mpa,断裂伸长率为33.67%。 0.20g (0.71mmol), styrene 0.10g (0.96mmol), acrylonitrile 0.20g (3.73mmol), 0.01g, divinylbenzene 0.02g, mix the solution evenly, apply it on the mold, irradiate with ultraviolet light (wavelength 240nm-380nm) for 30min, and polymerize in situ to form a film. Then soak the anion exchange membrane in 1M KOH solution at 60°C for 24 hours to convert the anions into OH - . The ion exchange capacity of the OH - type anion exchange membrane obtained in this example is 1.39 mmol/g, and the ion conductivity at room temperature is 2.75×10 -2 S·cm -1 , and the ion conductivity at 90°C is 5.16×10 -2 S·cm -1 . The tensile strength is 8.98Mpa, the Young's modulus is 621Mpa, and the elongation at break is 33.67%.
实施例九:Embodiment nine:
0.25g(1.07mmol),α-甲基丙烯腈0.10g(1.48mmol),α-甲基苯乙烯0.10g(0.85mmol),安息香乙醚0.01g,二乙烯基苯0.02g,将溶液混合均匀,涂到模具上,紫外光照(波长240nm-380nm)30min,原位聚合成膜。然后将该阴离子交换膜浸泡在60℃1M KOH溶液中24小时,将阴离子转换成OH-,本实施例获得的OH-型阴离子交换膜离子交换容量为1.78mmol/g,室温下离子传导率为3.06×10-2S·cm-1,90℃下离子传导率为6.53×10-2S·cm-1。抗张强度为11.41Mpa,杨氏模量为439.9Mpa,断裂伸长率为52.65%。 0.25g (1.07mmol), α-methacrylonitrile 0.10g (1.48mmol), α-methylstyrene 0.10g (0.85mmol), benzoin ether 0.01g, divinylbenzene 0.02g, mix the solution evenly, Apply to the mold, irradiate with ultraviolet light (wavelength 240nm-380nm) for 30 minutes, and polymerize in situ to form a film. Then soak the anion exchange membrane in 60°C 1M KOH solution for 24 hours to convert the anions into OH - . The ion exchange capacity of the OH - type anion exchange membrane obtained in this example is 1.78mmol/g, and the ion conductivity at room temperature is 3.06×10 -2 S·cm -1 , and the ion conductivity at 90°C is 6.53×10 -2 S·cm -1 . The tensile strength is 11.41Mpa, the Young's modulus is 439.9Mpa, and the elongation at break is 52.65%.
实施例十Embodiment ten
0.20g(0.65mmol),α-甲基丙烯腈0.20g(2.99mmol),α-甲基苯乙烯0.10g(0.85mmol),安息香乙醚0.02g,二乙烯基苯0.04g,将溶液混合均匀,涂到模具上,紫外光照(波长240nm-380nm)30min,原位聚合成膜。然后将该阴离子交换膜浸泡在60℃1M KOH溶液中,将阴离子转换成OH-,本实施例获得的OH-型阴离子交换膜离子交换容量为1.18mmol/g室温下离子传导率为2.69×10-2S·cm-1,90℃下离子传导率为5.28×10-2S·cm-1。抗张强度为25.13Mpa,杨氏模量为1041Mpa,断裂伸长率为13.22% 0.20g (0.65mmol), α-methacrylonitrile 0.20g (2.99mmol), α-methylstyrene 0.10g (0.85mmol), benzoin ethyl ether 0.02g, divinylbenzene 0.04g, mix the solution evenly, Apply to the mold, irradiate with ultraviolet light (wavelength 240nm-380nm) for 30 minutes, and polymerize in situ to form a film. Then soak the anion exchange membrane in 60°C 1M KOH solution to convert the anions into OH - . The ion exchange capacity of the OH - type anion exchange membrane obtained in this example is 1.18mmol/g and the ion conductivity at room temperature is 2.69×10 -2 S·cm -1 , the ion conductivity at 90°C is 5.28×10 -2 S·cm -1 . Tensile strength is 25.13Mpa, Young's modulus is 1041Mpa, elongation at break is 13.22%
实施例十一Embodiment Eleven
以实例二中所述比例制备的阴离子交换膜为样品,进行离子液体的聚合物阴离子交换膜的耐碱性测试,阴离子交换膜的耐碱性能测试参照文(Macromolecules 2010,43,3890-3896)所述方法,将阴离子交换膜浸泡到60℃的1M KOH溶液中,每隔一定时间取出膜,浸泡在去离子水中除净膜中残留的KOH,采用交流阻抗法测阴离子交换膜的离子传导率,温度范围为30℃~90℃。测试结果如图1所示,结果表明随着在碱液中浸泡时间的增加,阴离子交换膜的离子传导率并没有像传统阴离子交换膜一样出现下降的趋势。实验证明本发明制备的基于离子液体的聚合物阴离子交换膜有很好的耐碱性。Take the anion exchange membrane prepared in the ratio described in example two as sample, carry out the alkali resistance test of the polymer anion exchange membrane of ionic liquid, the alkali resistance performance test of anion exchange membrane is with reference to text (Macromolecules 2010,43,3890-3896) Described method, anion-exchange membrane is soaked in the 1M KOH solution of 60 ℃, takes out membrane at regular intervals, soaks in deionized water to remove residual KOH in the membrane, adopts AC impedance method to measure the ionic conductivity of anion-exchange membrane , the temperature range is 30 ° C ~ 90 ° C. The test results are shown in Figure 1, and the results show that with the increase of soaking time in alkaline solution, the ion conductivity of the anion exchange membrane does not show a downward trend like the traditional anion exchange membrane. Experiments prove that the polymer anion exchange membrane based on ionic liquid prepared by the invention has good alkali resistance.
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