CN110628021A - 一种侧链型磺化聚喹喔啉及其质子交换膜 - Google Patents
一种侧链型磺化聚喹喔啉及其质子交换膜 Download PDFInfo
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- 239000012528 membrane Substances 0.000 title abstract description 53
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical class N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 8
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- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000000446 fuel Substances 0.000 abstract description 7
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- -1 4-phenoxy (mercapto) phenyl Chemical group 0.000 description 14
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 8
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- 229910052751 metal Inorganic materials 0.000 description 4
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
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- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical group C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 description 2
- RQBIGPMJQUKYAH-UHFFFAOYSA-N 4-(3,4-diaminophenoxy)benzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1OC1=CC=C(N)C(N)=C1 RQBIGPMJQUKYAH-UHFFFAOYSA-N 0.000 description 2
- JKETWUADWJKEKN-UHFFFAOYSA-N 4-(3,4-diaminophenyl)sulfonylbenzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1S(=O)(=O)C1=CC=C(N)C(N)=C1 JKETWUADWJKEKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
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- 238000006467 substitution reaction Methods 0.000 description 2
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- QWNCDHYYJATYOG-UHFFFAOYSA-N 2-phenylquinoxaline Chemical class C1=CC=CC=C1C1=CN=C(C=CC=C2)C2=N1 QWNCDHYYJATYOG-UHFFFAOYSA-N 0.000 description 1
- URMNVIKGFSSFRC-UHFFFAOYSA-N 4-(3,4-diaminophenyl)sulfanylbenzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1SC1=CC=C(N)C(N)=C1 URMNVIKGFSSFRC-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ANUAIBBBDSEVKN-UHFFFAOYSA-N benzene-1,2,4,5-tetramine Chemical compound NC1=CC(N)=C(N)C=C1N ANUAIBBBDSEVKN-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0694—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring, e.g. polyquinoxalines
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Abstract
本发明公开了一种侧链型磺化聚喹喔啉及其质子交换膜的制备方法,属于质子交换膜领域。为解决芳香族磺化聚合物质子交换膜在高温下工作时质子传导率较低,化学稳定性较差的问题。采用如下技术方案,由具有明确可磺化位点的二偶酰单体,不可磺化的二偶酰单体和不同四胺单体按照不同摩尔比例共聚,并通过温和的后磺化法,得到磺化位置明确,离子交换容量可预测,结果可重复的侧链型磺化聚喹喔啉。本发明涉及的侧链型磺化聚喹喔啉的制备工艺简单,反应条件温和,磺化度可控,且所得的质子交换膜具有良好的质子传导率、优异的水解稳定性、尺寸稳定性和良好的燃料电池性能,作为燃料电池质子交换膜有极大的应用潜力。
Description
(2)技术领域
本发明属于质子交换膜领域,具体涉及一种侧链型磺化聚喹喔啉质子交换膜。
(3)背景技术
与当前的可再生燃料电源相比,质子交换膜燃料电池(PEMFC)能以更低的环境成本实现更高的效率。聚合物质子交换膜(PEM)在燃料电池系统中起着关键作用,既要隔离两电极间的燃料气体又要将质子从阳极转移到阴极[Feixiang Gong,Nanwen Li,SuoboZhang.Synthesis and properties of novel sulfonated poly(phenylquinoxaline)sas proton exchange membranes[J].Polymer.50(2009)6001–6008]。目前,全氟磺酸型PEM是唯一被商品化的质子交换膜,具有优良的质子传导能力、化学稳定性和机械性能,代表性的是美国Nafion系列的PEM。但是全氟磺酸型PEM成本高,工作的湿度、温度区间较窄,这限制了它们的广泛应用[Heitner-Wirguin C.Recent advances in perfluorinatedionomer membranes:structure,propert ies and applications[J].Journal ofMembrane Science,1996;120(1):1-33]。
为代替氟化聚合物电解质膜,使得成本和燃料渗透降低,并使燃料电池性能得到有效改善,已开发出非氟化芳烃PEM,如磺化聚砜、磺化聚苯硫醚、磺化聚醚醚酮、磺化聚苯并咪唑、磺化聚磷腈等。[Sho uwen Chen,Yan Yin,Hidetoshi Kita,KenichiOkamoto.Synthesis and Properties of Sulfonated Polyimid es from HomologousSulfonated Diamines Bearing Bis(aminophenoxyphenyl)sulfone[J].Journal ofPolymer Science Part A Polymer Chemistry,2007;45:2797-2811]。非氟磺酸型聚合物作为替代膜有价格相对低廉,在较宽温度范围内吸水率高,原材料对环境污染较小等优点。但其中大多数都未能满足高性能质子交换膜所需要的高操作温度下的高质子传导率,较强的水解稳定性和高持久稳定性[Asano N,Aoki M,Suzuki S, Miyatake K,Uchida H,Watanabe M.J Am Chem Soc2006;128:1762–9]。磺化聚喹喔啉类PEM作为非氟磺酸型PEM的代表,因其简单温和的反应条件,可控的磺化度而被作为替代膜,所得聚合物通常在DMA C和DMSO中具有良好的溶解度。
(4)发明内容
针对现有技术的不足,本发明提供了一种高水解稳定性、尺寸稳定性以及高质子传导性的利用后磺化法制备侧链型磺化聚喹喔啉及其质子交换膜的方法。
本发明提供的一种侧链型磺化聚喹喔啉质子交换膜,由具有质子传导性能的磺化结构单元(a)和无磺化位点的结构单元(b)通过共聚形成,其结构通式如下:
其中x和y分别为不同重复单元占整个聚合物的百分含量,x=0~100%,y=0~100%,且x+y=1。
R1为下述化学结构的一种:
(其中X为O或S其中的一种)
Ar1为下述化学结构的一种:
(其中X为O或S其中的一种)
Ar2为含有芳环的四胺,为下述物质中的一种:
(其中X为O或S其中的一种)
所述一种利用后磺化法制备的侧链型磺化聚喹喔啉及其质子交换膜的制备方法,具体包括以下步骤:
步骤一:将结构单元(a),(b)对应的按一定摩尔比例的二偶酰单体与四胺单体在适量的有机溶剂中进行聚合反应,得到非磺化聚喹喔啉,将聚喹喔啉溶液倒入沉淀剂中,聚合物析出,反复洗涤后烘干。
步骤二:将上述得到的聚喹喔啉,通过适量磺化试剂,在一定温度下进行后磺化,得到侧链型磺化聚喹喔啉。
步骤三:上述磺化聚喹喔啉溶液,在水中析出后,加入碱性试剂,至pH>7,过滤,洗涤至中性,收集固体,真空干燥,得到磺酸盐形式的磺化聚喹喔啉。
进一步的,所述的一种利用后磺化法制备的侧链型磺化聚喹喔啉的制备方法,其特征在于,组成磺化前聚喹喔啉结构单元(a)的单体为:4,4'-二(2-(4-苯氧(巯)基苯基)偶酰基)二苯(硫)醚,4,4'-二(2-(4-(4- 苯氧(巯)基苯基)苯基)偶酰基)二苯(硫)醚,4,4'-二(2-(4-(4-苯基苯氧(巯)基)苯基)偶酰基) 二苯(硫)醚,4,4'-二(2-(4-联苯基)偶酰基)二苯(硫)醚,4,4’-二(2-(4-苯氧(巯)基苯基)偶酰基)联苯,4,4’- 二(2-(4-(4-苯氧(巯)基苯基)苯基)偶酰基)联苯,4,4’-二(2-(4-(4-苯基苯氧(巯)基)苯基)偶酰基)联苯,4,4’-二(2-(4-联苯基)偶酰基)联苯,1,4-二(2-(4-苯氧(巯)基苯基)偶酰基)苯,1,4-二(2-(4-(4-苯氧(巯)基苯基) 苯基)偶酰基)苯,1,4-二(2-(4-(4-苯基苯氧(巯)基)苯基)偶酰基)苯,1,4-二(2-(4-联苯基)偶酰基)苯,4,4'- 二(2-(4-苯氧(巯)基苯基)偶酰基)二苯砜,4,4'-二(2-(4-(4-苯氧(巯)基苯基)苯基)偶酰基)二苯砜,4,4'-二 (2-(4-(4-苯基苯氧(巯)基)苯基)偶酰基)二苯砜,4,4'-二(2-(4-联苯基)偶酰基)二苯砜中的一种。
进一步的,所述的一种利用后磺化法制备的侧链型磺化聚喹喔啉的制备方法,其特征在于,组成磺化前聚喹喔啉结构单元(b)的单体为:联苯偶酰,1,4-二(苯乙二酰基)苯,4,4'-苯偶酰基氧(硫),4,4’-苯偶酰基砜中的一种。。
进一步的,所述的一种利用后磺化法制备的侧链型磺化聚喹喔啉的制备方法,其特征在于,含有芳环的四胺为:3,3',4,4'-四氨基联苯,1,2,4,5-苯四胺,3,3',4,4'-四氨基二苯(硫)醚,2-氨基-4-((3,4-二氨基苯基)磺酰基)苯胺中的一种。
本发明还提供一种利用后磺化法制备的侧链型磺化聚喹喔啉质子交换膜的制备方法,包括以下步骤:
将所得聚合物溶于非质子性溶剂中,过滤,脱泡,将溶液缓慢浇铸在超平玻璃皿上,60~100℃恒温12h 以上,随后升温100℃以上继续恒温4小时,结束后向玻璃皿中加入足量去离子水脱膜,将膜取出浸泡在 1mol/L的酸溶液中,充分交换后取出并用去离子水洗净干燥,得到其质子交换膜。
本发明的有益效果是:反应条件简单温和,磺化度可控,所得聚合物通常在DMAC和DMSO中有良好的溶解度。并且在很宽的温度范围内都具有优异的热水解稳定性和良好的尺寸稳定性,这正是PEM所需的属性。
(5)具体实施方式
实施例1:
本实施例以四胺(4)骨架,以磺化前聚喹喔啉结构单元(a)的单体(7)为原料合成磺化聚喹喔啉为例,结构如下:
具体制备方法为:
(1)聚合
分别称4,4’-二(2-(4-(4-苯基苯氧基)苯基)偶酰基)联苯0.7551g和2-氨基-4-((3,4-二氨基苯基)磺酰基) 苯胺0.2802g,混合后倒入烧瓶,加入间甲酚溶解,在氮气氛围下室温反应约24h,将溶液倒入乙醇中使聚合物析出,反复洗涤直至洗净,过滤,收集固体,真空干燥,得到聚合物纤维。
(2)磺化
将聚合物纤维倒入烧瓶,以固含量为10~15wt%的比例加入发烟硫酸,在氮气氛围下反应,将液体倒入水中,磺化产物析出,反复洗涤至pH=3~4,加入适量碳酸钠,继续洗涤至中性,过滤收集固体,真空干燥,得到金属盐形式的磺化聚合物。
(3)制备质子交换膜;
将磺化后的聚合物按5wt%的比例溶于DMSO中,抽滤,脱泡,将滤液缓慢浇铸在超平玻璃皿上,低温恒温12h,随后高温恒温4h,结束后向皿中加入去离子水脱膜,将膜取出浸泡在1mol/L硫酸溶液中,与H+充分置换后将膜取出并用去离子水洗尽硫酸,干燥,得到质子交换膜。
实施例2:
本实施例以四胺(1)骨架,以磺化前聚喹喔啉结构单元(a)的单体(2)和结构单元(b)的单体 (3)为原料合成磺化聚喹喔啉为例,结构如下(其中x:y=4:1):
具体制备方法为:
(1)聚合
称取4,4'-二(2-(4-(4-苯氧基苯基)苯基)偶酰基)二苯醚1.2335g,联苯偶酰0.1741g和3,3’,4,4’-四氨基联苯0.4285g,在间甲酚中反应,反应结束后将溶液倒入乙醇中使聚合物析出反复洗涤至洗净,过滤,干燥,得到聚合物纤维。
(2)磺化
将所得聚合物与浓硫酸反应,反应结束后将溶液倒入水中,磺化产物析出,反复洗涤至pH=3~4,加入适量碳酸钠,继续洗涤至中性,过滤,干燥,得到金属盐形式的磺化聚合物。
(3)制备质子交换膜;
将磺化后的聚合物溶于DMSO中,抽滤,脱泡,将滤液缓慢浇铸在超平玻璃皿上,低温恒温12h,随后升温继续恒温4h,结束后向皿中加入水脱膜,将膜取出浸泡在1mol/L硫酸溶液中,与H+充分置换后将膜取出并洗净,干燥,得到质子交换膜。
实施例3:
本实施例以四胺(3)骨架,以磺化前聚喹喔啉结构单元(a)的单体(5)和结构单元(b)的单体 (3)为原料合成磺化聚喹喔啉为例,结构如下(其中x:y=4:1):
具体制备方法为:
(1)聚合
称取4,4’-二(2-(4-苯氧基苯基)偶酰基)联苯0.9643g,4,4'-苯偶酰基氧0.1739g和3,3',4,4'-四氨基二苯醚 0.4695g,在间甲酚中反应,反应结束后将溶液倒入乙醇中使聚合物析出反复洗涤至洗净,过滤,干燥,得到聚合物纤维。
(2)磺化
将所得聚合物与浓硫酸反应,反应结束后将溶液倒入水中,磺化产物析出,反复洗涤至pH=3~4,加入适量碳酸钠,继续洗涤至中性,过滤,干燥,得到金属盐形式的磺化聚合物。
(3)制备质子交换膜;
将磺化后的聚合物溶于DMSO中,抽滤,脱泡,将滤液缓慢浇铸在超平玻璃皿上,低温恒温12h,随后升温继续恒温4h,结束后向皿中加入水脱膜,将膜取出浸泡在1mol/L硫酸溶液中,与H+充分置换后将膜取出并洗净,干燥,得到质子交换膜。
实施例4:
本实施例以四胺(3)骨架,以磺化前聚喹喔啉结构单元(a)的单体(9)和结构单元(b)的单体 (3)为原料合成磺化聚喹喔啉为例,结构如下(其中x:y=4:1):
具体制备方法为:
(1)聚合
称取1,4-二(2-(4-苯氧基苯基)偶酰基)苯0.8427g,4,4'-苯偶酰基氧0.1800g和3,3',4,4'-四氨基二苯醚 0.4688g,在间甲酚中反应,反应结束后将溶液倒入乙醇中使聚合物析出反复洗涤至洗净,过滤,干燥,得到聚合物纤维。
(2)磺化
将所得聚合物与浓硫酸反应,反应结束后将溶液倒入水中,磺化产物析出,反复洗涤至pH=3~4,加入适量碳酸钠,继续洗涤至中性,过滤,干燥,得到金属盐形式的磺化聚合物。
(3)制备质子交换膜;
将磺化后的聚合物溶于DMSO中,抽滤,脱泡,将滤液缓慢浇铸在超平玻璃皿上,低温恒温12h,随后升温继续恒温4h,结束后向皿中加入水脱膜,将膜取出浸泡在1mol/L硫酸溶液中,与H+充分置换后将膜取出并洗净,干燥,得到质子交换膜。
(6)附图说明
图1为实施例1的核磁分析图
图2为实施例1,4的红外光谱图
图3为各实施例所述的侧链型磺化聚喹喔啉质子交换膜的性能。
Claims (4)
1.一种侧链型磺化聚喹喔啉,其特征在于:由具有明确的可磺化位点的二偶酰单体,不可磺化的二偶酰单体和不同四胺单体按照不同摩尔比例共聚、经过温和的后磺化法制备得到磺化位点精确可控的具有磺酸基团的结构单元(a)和非磺化的结构单元(b)的聚合物,其结构通式如下:
其中,x和y分别为不同重复单元占整个聚合物的摩尔百分含量,x=0%~100%,y=100%~0%,且x+y=1,
所述通式中的R1为下述化学结构中任意一种:
(其中X为O或S其中的一种)
所述通式中的Ar1为下述化学结构中任意一种:
(其中X为O或S其中的一种)
所述通式中的Ar2为下述化学结构中任意一种:
2.根据权利要求1所述的侧链型磺化聚喹喔啉,其特征在于,通过后磺化法,对上述制备的聚喹喔啉进行磺化,得到磺化聚喹喔啉,其中制备结构单元(a)所对应的具有明确磺化位点的二偶酰单体为以下结构中的任意一种:
(其中X为O或S)
3.根据权利要求1所述的一种侧链型磺化聚喹喔啉,其特征在于,制备磺化聚喹喔啉结构单元(b)的二偶酰单体为以下结构中的任意一种:
4.根据权利要求1所述的一种侧链型磺化聚喹喔啉,其特征在于,制备磺化聚喹喔啉,所需的含有芳环的四胺为以下结构中的任意一种:
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