CN111732717A - 含有聚芳哌啶基侧链的聚合物、制备方法及阴离子交换膜、制备方法 - Google Patents
含有聚芳哌啶基侧链的聚合物、制备方法及阴离子交换膜、制备方法 Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- 125000005936 piperidyl group Chemical group 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 150000003053 piperidines Chemical class 0.000 claims description 20
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
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- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 13
- 229920006254 polymer film Polymers 0.000 claims description 13
- 239000012716 precipitator Substances 0.000 claims description 13
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- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 11
- GUBPSDHTFMBJDC-UHFFFAOYSA-N piperidine-2,4-dione hydrochloride Chemical compound C1CNC(=O)CC1=O.Cl GUBPSDHTFMBJDC-UHFFFAOYSA-N 0.000 claims description 11
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 11
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical compound CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 claims description 9
- -1 hydroxide ions Chemical class 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
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- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 3
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
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- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229920005597 polymer membrane Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- QBVHMPFSDVNFAY-UHFFFAOYSA-N 1,1,1-trifluorobutan-2-one Chemical compound CCC(=O)C(F)(F)F QBVHMPFSDVNFAY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 2
- KZJRKRQSDZGHEC-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanone Chemical compound FC(F)(F)C(=O)C1=CC=CC=C1 KZJRKRQSDZGHEC-UHFFFAOYSA-N 0.000 description 2
- 229940087189 2,2,2-trifluoroacetophenone Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 238000011031 large-scale manufacturing process Methods 0.000 description 2
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- 238000012544 monitoring process Methods 0.000 description 2
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- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- ANCPETUIOVZOBQ-UHFFFAOYSA-N 3-fluoroheptan-2-one Chemical compound CCCCC(F)C(C)=O ANCPETUIOVZOBQ-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
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- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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Abstract
Description
技术领域
本发明涉及阴离子交换膜技术领域,特别是涉及一种含有聚芳哌啶基侧链的聚合物、制备方法及阴离子交换膜、制备方法。
背景技术
随着人们对能源需求的日益增长,开发可重复利用、能量转化效率高、环境污染小的新能源技术成为国内外研究的热点之一。燃料电池具有能量转化率高(50%~70%)、环境污染少、燃料来源广泛等优点,被认为是21世纪最具有发展前景的高效清洁发电技术之一。相比于质子交换膜燃料电池,阴离子交换膜燃料电池(AEMFC)的阴极还原速率高,且碱性介质允许使用非贵金属催化剂,大幅降低了燃料电池成本,因而受到广泛关注。然而,作为燃料电池关键组件之一的阴离子交换膜仍存在离子电导率低、化学稳定性差等问题,制约了AEMFC的商业化应用。
发明内容
基于此,有必要针对目前传统技术的问题,提供一种含有聚芳哌啶基侧链的聚合物,使用不含醚键的聚芳哌啶作为聚合物主链,且密集功能基团使得离子电导率较高,可满足燃料电池稳定运行的需求。
本发明还提供了上述含有聚芳哌啶基侧链的聚合物的制备方法,以及采用上述含有聚芳哌啶基侧链的聚合物制成的阴离子交换膜与阴离子交换膜的制备方法。
一种含有聚芳哌啶基侧链的聚合物,其化学结构式为:
本发明的有益效果如下:本发明含有聚芳哌啶基侧链的聚合物含有密集功能基团,使其成膜后可在膜内形成微相分离结构,构建高效的离子传输通道,允许离子在通道内快速传导,从而提高了离子传输效率;主链上不含醚键,有利于成膜后保持化学稳定;其制成的阴离子交换膜具有较高的离子电导率和优异的化学稳定性。
对上述方案的进一步改进为,R1为以下任意一种:
上述含有聚芳哌啶基侧链的聚合物的制备方法,采用的聚合条件温和的酸催化缩聚反应合成聚芳哌啶,反应条件简单,有利于进行大规模生产,该制备方法包括以下步骤:
将含苯环单体、三氟基酮、4-氧代哌啶酮盐酸盐溶于第一溶剂,随后加入三氟甲磺酸,在预设温度下搅拌反应,冷却至室温,在第一沉淀剂中析出,经过滤、洗涤、干燥,得到聚芳哌啶;
将1-甲基哌啶和1,6-二溴己烷溶于第二溶剂,充分反应,经过滤、洗涤、干燥,得到哌啶盐;
将聚芳哌啶和哌啶盐溶于有机溶剂,加入N,N'-二异丙基乙胺,充分反应,冷却至室温,在第二沉淀剂中析出,经过滤、洗涤、干燥,得到含有聚芳哌啶基侧链的聚合物。
对上述方案的进一步改进为,第一溶剂为二氯甲烷。
对上述方案的进一步改进为,第二溶剂为四氢呋喃、二甲基亚砜、N-甲基吡咯烷酮、二甲基甲酰胺、甲醇、乙醇和丙醇中的一种。
对上述方案的进一步改进为,含苯环单体、三氟基酮、4-氧代哌啶酮盐酸盐和三氟甲磺酸的摩尔比为1:(0.1~3):(0.1~3):(0.1~100)。
对上述方案的进一步改进为,第一沉淀剂为无水乙醚、甲醇、乙醇、水和氨水中的任一种。
对上述方案的进一步改进为,1-甲基哌啶、1,6-二溴己烷的摩尔比是1:(0.1~20)。
对上述方案的进一步改进为,第二溶剂与1-甲基哌啶的摩尔比为(1~100):1。
对上述方案的进一步改进为,聚芳哌啶:哌啶盐:N,N'-二异丙基乙胺的摩尔比为(0~1):(0~10):(0.1~10)。
对上述方案的进一步改进为,有机溶剂为二甲基亚砜、N-甲基吡咯烷酮、二甲基甲酰胺;第二沉淀剂为无水乙醚、丙酮、石油醚和甲基叔丁基醚中的任一种。
一种阴离子交换膜,采用上述含有聚芳哌啶基侧链的聚合物制成。
上述阴离子交换膜的的制备方法,包括以下步骤:
将含有聚芳哌啶基侧链的聚合物溶于第三溶剂,得到铸膜液;
将铸膜液涂覆于基材上,在室温~140℃下挥发第三溶剂,得到含有聚芳哌啶基侧链的聚合物膜;
在0℃~80℃下,将含有聚芳哌啶基侧链的聚合物膜浸泡于0.05~4mol/L碱溶液中,使含有聚芳哌啶基侧链的聚合物膜中的阴离子转换成氢氧根离子,得到阴离子交换膜。
附图说明
图1为实施例1制备的阴离子交换膜的示意图;
图2为图1阴离子交换膜的核磁共振氢谱图。
具体实施方式
为了便于理解本发明,下面将对本发明进行更全面的描述。但是,本发明可以以许多不同的形式来实现,并不限于本文所描述的实施例。相反地,提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的,不是旨在于限制本发明。
本发明提供了一种含有聚芳哌啶基侧链的聚合物,其化学结构式为:
本发明含有聚芳哌啶基侧链的聚合物含有密集功能基团,使其成膜后可在膜内形成微相分离结构,构建高效的离子传输通道,允许离子在通道内快速传导,从而提高了离子传输效率;主链上不含醚键,有利于成膜后保持化学稳定;其制成的阴离子交换膜具有较高的离子电导率和优异的化学稳定性。
进一步地,R1为以下任意一种:
上述含有聚芳哌啶基侧链的聚合物的制备方法包括以下步骤:
S100:将含苯环单体、三氟基酮、4-氧代哌啶酮盐酸盐溶于第一溶剂,随后加入三氟甲磺酸,在预设温度下搅拌反应,冷却至室温,在第一沉淀剂中析出,经过滤、洗涤、干燥,得到聚芳哌啶。
加入三氟甲磺酸后,温度调至-5℃~60℃,在-5℃~60℃下搅拌反应,反应完全后,冷却至室温,得到反应液。将反应液加入第一沉淀剂中,析出聚芳哌啶粗产品固体,聚芳哌啶粗产品固体经过滤、洗涤、干燥,得到聚芳哌啶。
含苯环单体、三氟基酮、4-氧代哌啶酮盐酸盐和三氟甲磺酸的摩尔比为1:(0.1~3):(0.1~3):(0.1~100)。具体地,苯环单体的物质的量等于三氟基酮和4-氧代哌啶酮盐酸盐的物质的量总和。
根据R1的结构,含苯环单体可以选为联二苯、间三联苯或对三联苯。根据R2的结构,三氟基酮可选用1,1,1-三氟丙酮、1,1,1-三氟-2-丁酮、3-氟-2-庚酮或2,2,2-三氟苯乙酮等。
较优地,含苯环单体与第一溶剂的摩尔比为1:(1~200)。第一溶剂可以为二氯甲烷。
第一沉淀剂为无水乙醚、甲醇、乙醇、水和氨水中的任一种。
S200:将1-甲基哌啶和1,6-二溴己烷溶于第二溶剂,充分反应,经过滤、洗涤、干燥,得到哌啶盐。
1-甲基哌啶和1,6-二溴己烷的反应温度可以为室温~100℃,可选用的温度较宽,有利于根据实际情况选择合适的实验温度,在反应过程中不需要太精细的温度监控,降低生产强度。
1-甲基哌啶和1,6-二溴己烷的摩尔比是1:(0.1~20),第二溶剂与1-甲基哌啶的摩尔比为(1~100):1。
第二溶剂可以为四氢呋喃、二甲基亚砜、N-甲基吡咯烷酮、二甲基甲酰胺、甲醇、乙醇和丙醇中的一种。
S300:将聚芳哌啶和哌啶盐溶于有机溶剂,加入N,N'-二异丙基乙胺,充分反应,冷却至室温,在第二沉淀剂中析出,经过滤、洗涤、干燥,得到含有聚芳哌啶基侧链的聚合物。
聚芳哌啶、哌啶盐和N,N'-二异丙基乙胺的反应温度为室温~100℃,可选用的温度较宽,有利于根据实际情况选择合适的实验温度,在反应过程中不需要太精细的温度监控,降低生产强度。
聚芳哌啶、哌啶盐和N,N'-二异丙基乙胺反应完全后,冷却至室温,得到混合液,将混合液加入第二沉淀剂中,析出聚合物粗产品固体,聚合物粗产品固体经过过滤、洗涤、干燥,得到含有聚芳哌啶基侧链的聚合物。
聚芳哌啶、哌啶盐和N,N'-二异丙基乙胺的摩尔比为(0~1):(0~10):(0.1~10),较优地,聚芳哌啶、哌啶盐和N,N'-二异丙基乙胺的摩尔比为(0.1~1):(0.1~10):(0.1~10)。聚芳哌啶与有机溶剂的摩尔比为1:(1~100)。
有机溶剂为二甲基亚砜、N-甲基吡咯烷酮和二甲基甲酰胺中的一种。
第二沉淀剂为无水乙醚、丙酮、石油醚和甲基叔丁基醚中的一种。
采用的聚合条件温和的酸催化缩聚反应合成聚芳哌啶,反应条件简单,在较低温度下即可进行,有利于进行大规模生产。
本发明含有聚芳哌啶基侧链的聚合物可制成阴离子交换膜,聚合物的主链上不含醚键,有利于膜的保持化学稳定,且阴离子交换膜具有较高的离子电导率。
上述阴离子交换膜的制备方法,包括以下步骤:
将含有聚芳哌啶基侧链的聚合物溶于第三溶剂,得到铸膜液。第三溶剂可以为二甲基亚砜、N-甲基吡咯烷酮或二甲基甲酰胺。
将铸膜液涂覆于基材上,在室温~140℃下挥发第三溶剂,得到含有聚芳哌啶基侧链的聚合物膜。基材可以为阴离子交换膜常见的基材。
在0℃~80℃下,将含有聚芳哌啶基侧链的聚合物膜浸泡于0.05~4mol/L碱溶液中,使含有聚芳哌啶基侧链的聚合物膜中的阴离子转换成氢氧根离子,得到阴离子交换膜。
碱溶液为含有氢氧根离子的溶液,如氢氧化钾或氢氧化钠溶液,氢氧根离子的电离度较高,有利于促进阴离子交换。
以下为具体实施例说明。
实施例1
本实施例的含有聚芳哌啶基侧链的聚合物的化学结构式如下:
本实施例阴离子交换膜的制备方法为先制备含有聚芳哌啶基侧链的聚合物,然后采用含有聚芳哌啶基侧链的聚合物制备阴离子交换膜,则阴离子交换膜的制备方法包括以下步骤:
S100:将2.00g间三联苯、1.09g 2,2,2-三氟苯乙酮、0.56g 4-氧代哌啶酮盐酸盐溶于100mL二氯甲烷,随后加入7mL三氟甲磺酸,在室温下反应48h,在甲醇中沉淀析出,经过滤、洗涤、干燥,得到聚芳哌啶。
S200:将2g 1-甲基哌啶和25mL 1,6-二溴己烷溶于100mL的四氢呋喃,在60℃反应12h,经过滤、洗涤、干燥固体,得到哌啶盐。
S300:将2g聚芳哌啶和2.5g哌啶盐溶于二甲基亚砜,加入1mL N,N'-二异丙基乙胺,在70℃反应24h,冷却至室温,在无水乙醚中析出,经过滤、洗涤、干燥,得到含有聚芳哌啶基侧链的聚合物。
S400:在室温下,将1g含有聚芳哌啶基侧链的聚合物溶于25mL二甲基亚砜,得到铸膜液。
S500:将铸膜液涂覆于平板基材,在60℃下挥发二甲基亚砜24h,得到含有聚芳哌啶基侧链的聚合物膜。
S600:在室温下,将含有聚芳哌啶基侧链的聚合物膜浸泡于1mol/L氢氧化钾48h,使膜中的阴离子转换成氢氧根离子,得到阴离子交换膜,如图1所示。
实施例2
本实施例的聚芳哌啶基侧链型阴离子交换膜,化学结构式如下:
本实施例阴离子交换膜的制备方法为先制备含有聚芳哌啶基侧链的聚合物,然后采用含有聚芳哌啶基侧链的聚合物制备阴离子交换膜,则阴离子交换膜的制备方法包括以下步骤:
S100:将2.00g对三联苯、0.57g 1,1,1-三氟-2-丁酮、0.56g 4-氧代哌啶酮盐酸盐溶于50mL二氯甲烷,随后加入10mL三氟甲磺酸,在室温下反应72h,在甲醇中沉淀析出,经过滤、洗涤、干燥,得到聚芳哌啶。
S200:将4g 1-甲基哌啶和50mL 1,6-二溴己烷溶于200mL的四氢呋喃,在70℃反应24h,经过滤、洗涤、干燥固体,得到哌啶盐。
S300:将1g聚芳哌啶和1.5g哌啶盐溶于二甲基亚砜,加入3mL N,N'-二异丙基乙胺,在90℃反应24h,冷却至室温,在无水乙醚中析出,经过滤、洗涤、干燥,得到含有聚芳哌啶基侧链的聚合物。
S400:在室温下,将2g含有聚芳哌啶基侧链的聚合物溶于50mL二甲基亚砜,得到铸膜液。
S500:将铸膜液涂覆于平板基材上,在100℃下挥发二甲基亚砜4h,得到含有聚芳哌啶基侧链的聚合物膜。
S600:在室温下,将含有聚芳哌啶基侧链的聚合物膜浸泡于0.5mol/L氢氧化钾72h,使膜中的阴离子转换成氢氧根离子,得到阴离子交换膜。
实施例3
本实施例的聚芳哌啶基侧链型阴离子交换膜,化学结构式如下:
本实施例阴离子交换膜的制备方法为先制备含有聚芳哌啶基侧链的聚合物,然后采用含有聚芳哌啶基侧链的聚合物制备阴离子交换膜,则阴离子交换膜的制备方法包括以下步骤:
S100:将1.37g对联二苯、0.6g 1,1,1-三氟-2-丁酮、0.56g 4-氧代哌啶酮盐酸盐溶于100mL二氯甲烷,随后加入20mL三氟甲磺酸,在室温下反应72h,在甲醇中沉淀析出,经过滤、洗涤、干燥,得到聚芳哌啶。
S200:将5g 1-甲基哌啶和50mL 1,6-二溴己烷溶于300mL的四氢呋喃,在70℃反应24h,经过滤、洗涤、干燥固体,得到哌啶盐。
S300:将3g聚芳哌啶和2g哌啶盐溶于二甲基亚砜,加入5mL N,N'-二异丙基乙胺,在90℃反应24h,冷却至室温,在无水乙醚中析出,经过滤、洗涤、干燥,得到含有聚芳哌啶基侧链的聚合物。
S400:在室温下,将2.5g含有聚芳哌啶基侧链的聚合物溶于50mL二甲基亚砜,得到铸膜液。
S500:将铸膜液涂覆于平板基材上,在100℃下挥发二甲基亚砜5h,得到含有聚芳哌啶基侧链的聚合物膜。
S600:在室温下,将含有聚芳哌啶基侧链的聚合物膜浸泡于1.0mol/L氢氧化钾72h,使膜中的阴离子转换成氢氧根离子,得到阴离子交换膜。
实施例4
本实施例的聚芳哌啶基侧链型阴离子交换膜,化学结构式如下:
本实施例阴离子交换膜的制备方法为先制备含有聚芳哌啶基侧链的聚合物,然后采用含有聚芳哌啶基侧链的聚合物制备阴离子交换膜,则阴离子交换膜的制备方法包括以下步骤:
S100:将5.38g对联二苯、3.01g 1,1,1-三氟丙酮、1.10g 4-氧代哌啶酮盐酸盐溶于100mL二氯甲烷,随后加入16mL三氟甲磺酸,在室温下反应60h,在甲醇中沉淀析出,经过滤、洗涤、干燥,得到聚芳哌啶。
S200:将4g 1-甲基哌啶和45mL 1,6-二溴己烷溶于300mL的N-甲基吡咯烷酮,在30℃反应36h,经过滤、洗涤、干燥固体,得到哌啶盐。
S300:将0.5g聚芳哌啶和5g哌啶盐溶于N-甲基吡咯烷酮,加入10mL N,N'-二异丙基乙胺,在90℃反应24h,冷却至室温,在石油醚中析出,经过滤、洗涤、干燥,得到含有聚芳哌啶基侧链的聚合物。
S400:在室温下,将5g含有聚芳哌啶基侧链的聚合物溶于80mL二甲基亚砜,得到铸膜液。
S500:将铸膜液涂覆于平板基材上,在130℃下挥发二甲基亚砜10h,得到含有聚芳哌啶基侧链的聚合物膜。
S600:在室温下,将含有聚芳哌啶基侧链的聚合物膜浸泡于0.1mol/L氢氧化钾85h,使膜中的阴离子转换成氢氧根离子,得到阴离子交换膜。
对实施例1的阴离子交换膜进行核磁共振检测,其核磁共振氢谱如图2所示。
对实施例1至4的阴离子交换膜分别检测其在80℃温度下的离子电导率和在60℃温度下,于2mol/L的KOH溶液浸泡96h后,采用核磁共振光谱和傅里叶红外光谱检测阴离子交换膜中含有聚芳哌啶基侧链的聚合物的化学结构变化,检测结果如表1。其中,对比例为目前文献报道的阴离子交换膜的离子电导率。
表1
离子电导率(mS·cm<sup>-1</sup>) | 化学结构有无变化 | |
实施例1 | 125.1 | 无变化 |
实施例2 | 122.6 | 无变化 |
实施例3 | 125.3 | 无变化 |
实施例4 | 120.0 | 无变化 |
对比例 | ≤100 | — |
由表1可知,本发明的阴离子交换膜的离子电导率达120mS·cm-1以上,远高于目前文献报道的阴离子交换膜的离子电导率,且在60℃温度下,于2mol/L的KOH溶液浸泡96h后,阴离子交换膜中含有聚芳哌啶基侧链的聚合物的化学结构不变,则阴离子交换膜具有良好的化学稳定性,有助于本发明阴离子交换膜的商业化应用。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (10)
3.一种如权利要求1或2所述的含有聚芳哌啶基侧链的聚合物的制备方法,其特征在于,所述制备方法包括以下步骤:
将含苯环单体、三氟基酮、4-氧代哌啶酮盐酸盐溶于第一溶剂,随后加入三氟甲磺酸,在预设温度下搅拌反应,冷却至室温,在第一沉淀剂中析出,经过滤、洗涤、干燥,得到聚芳哌啶;
将1-甲基哌啶和1,6-二溴己烷溶于第二溶剂,充分反应,经过滤、洗涤、干燥,得到哌啶盐;
将所述聚芳哌啶和哌啶盐溶于有机溶剂,加入N,N'-二异丙基乙胺,充分反应,冷却至室温,在第二沉淀剂中析出,经过滤、洗涤、干燥,得到含有聚芳哌啶基侧链的聚合物。
4.根据权利要求3所述的含有聚芳哌啶基侧链的聚合物的制备方法,其特征在于,所述含苯环单体、三氟基酮、4-氧代哌啶酮盐酸盐和三氟甲磺酸的摩尔比为1:(0.1~3):(0.1~3):(0.1~100)。
5.根据权利要求3或4所述的含有聚芳哌啶基侧链的聚合物的制备方法,其特征在于,所述第一沉淀剂为无水乙醚、甲醇、乙醇、水和氨水中的任一种。
6.根据权利要求3所述的含有聚芳哌啶基侧链的聚合物的制备方法,其特征在于,所述1-甲基哌啶、1,6-二溴己烷的摩尔比是1:(0.1~20)。
7.根据权利要求3所述的含有聚芳哌啶基侧链的聚合物的制备方法,其特征在于,所述聚芳哌啶:哌啶盐:N,N'-二异丙基乙胺的摩尔比为(0~1):(0~10):(0.1~10)。
8.根据权利要求3所述的含有聚芳哌啶基侧链的聚合物的制备方法,其特征在于,所述有机溶剂为二甲基亚砜、N-甲基吡咯烷酮、二甲基甲酰胺;所述第二沉淀剂为无水乙醚、丙酮、石油醚和甲基叔丁基醚中的任一种。
9.一种阴离子交换膜,其特征在于,采用权利要求1或2的含有聚芳哌啶基侧链的聚合物制成。
10.一种如权利要求9所述的阴离子交换膜的制备方法,其特征在于,包括以下步骤:
将所述含有聚芳哌啶基侧链的聚合物溶于第三溶剂,得到铸膜液;
将所述铸膜液涂覆于基材上,在室温~140℃下挥发所述第三溶剂,得到含有聚芳哌啶基侧链的聚合物膜;
在0℃~80℃下,将所述含有聚芳哌啶基侧链的聚合物膜浸泡于0.05~4mol/L碱溶液中,使所述含有聚芳哌啶基侧链的聚合物膜中的阴离子转换成氢氧根离子,得到阴离子交换膜。
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