新型双功能交联型阴离子交换膜的制备与性能

doi:10.7503/cjcu20180049

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (9): 2054.doi: 10.7503/cjcu20180049

新型双功能交联型阴离子交换膜的制备与性能

管明明, 陈佳, 唐韶坤()

天津大学化工学院绿色合成与转化教育部重点实验室, 天津化学化工协同创新中心, 天津300354

收稿日期:2018-01-15 出版日期:2018-05-16 发布日期:2018-05-16
作者简介:
联系人简介: 唐韶坤, 女, 博士, 教授, 主要从事功能材料的合成及应用研究. E-mail: shktang@tju.edu.cn
基金资助:
国家自然科学基金(批准号: 21328601)资助.

Synthesis and Performance of Novel Bis-functional Cross-linked Anion Exchange Membranes^†

GUAN Mingming, CHEN Jia, TANG Shaokun^*()

Key Laboratory for Green Chemical Technology, Ministry of Education, School of Chemical Engineering & Technology, Collaborative Innovation Center of Chemical Center of Chemical Science and Engineering(Tianjin), Tianjin University, Tianjin 300354, China

Received:2018-01-15 Online:2018-05-16 Published:2018-05-16
Contact: TANG Shaokun E-mail:shktang@tju.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.21328601).

摘要/Abstract

摘要：

以2-甲基咪唑为原料合成2种离子液体前驱体1-烯丙基-2-甲基咪唑和1-丁基-2-甲基咪唑, 以苯乙烯(St)和对氯甲基苯乙烯(VBC)为原料制备聚离子液体主链p(St-co-VBC), 2种离子液体前驱体与聚离子液体主链发生季铵化反应铸膜, 制备了交联结构和梳型侧链结构型阴离子交换膜(AEMs). 通过傅里叶红外光谱、扫描电子显微镜和热重分析等考察了阴离子交换膜的结构、微观形貌、氢氧根离子传导率、热稳定性及碱性稳定性等性能. 结果表明, AEMs含水率为36.7%~93.4%, 离子交换容量为1.61~2.16 mmol/g, 80 ℃时, p(St-co-VBC)-3型AEMs氢氧根离子传导率高达68.4 mS/cm, 在1 mol/L NaOH溶液中碱性浸泡240 h后, 氢氧根离子传导率仍高达52.2 mS/cm, 具备良好的碱性稳定性.

关键词: 双功能交联, 梳型结构, 阴离子交换膜, 氢氧根离子传导率, 耐碱性

Abstract:

A polymerized ionic liquid copolymer composed of two ionic liquid precursors, 1-allyl-2-methylimidazole and 1-butyl-2-methylimidazole, and a poly(ionic liquid) main chain p(St-co-VBC) were synthesized via quaternization reaction to prepare anion exchange membranes(AEMs). The two ionic liquid precursors were synthesized from 2-methylimidazole. The poly(ionic liquid) main chain was prepared from styene(St) and p-chloromethylstyrene(VBC). The prepared membranes possessed crosslinked and comb shaped side-chain structure. Fourier transform infrared, scanning electron microscopy and thermogravimetry were used to investigate the molecule structure, morphology, hydroxide conductivity, thermal stability, alkaline stability and other properties of the membranes. The results showed that the AEMs had quite low water uptake, 36.7%—93.4%, and the ion exchange capacity was 1.61—2.16 mmol/g. The conductivity of p(St-co-VBC)-3 AEMs was as high as 68.4 mS/cm at 80 ℃. The AEMs displayed excellent alkaline stability and the hydroxide conductivity of p(St-co-VBC)-3 AEMs was still as high as 52.2 mS/cm after immersing in 1 mol/L NaOH solution for 240 h.

Key words: Bis-functional cross-linked, Comb-shaped structure, Anion exchange membrane, Hydroxide conductivity, Alkaline stability

中图分类号:

O631.5

TrendMD:

管明明, 陈佳, 唐韶坤. 新型双功能交联型阴离子交换膜的制备与性能. 高等学校化学学报, 2018, 39(9): 2054.

GUAN Mingming,CHEN Jia,TANG Shaokun. Synthesis and Performance of Novel Bis-functional Cross-linked Anion Exchange Membranes^†. Chem. J. Chinese Universities, 2018, 39(9): 2054.

图/表 13

Scheme 1 Synthesis of 1-butyl-2-methylimidazole

Scheme 2 Preparation of 1-allyl-2-methylimidazole

Scheme 3 Synthetic procedure for bis-functional cross-linked AEMs

Fig.1 GPC chromatograms of synthesized p(St-co-VBC)-x[x=3(a), 4(b), 5(c)]

Fig.2 TGA curves of p(St-co-VBC)-x [x=3(a), 4(b), 5(c)]

Fig.3 Photograph of the AEMs(A), low(B) and high(C) magnification cross-sectional SEM images of AEMs

Fig.4 FTIR spectra of p(St-co-VBC)-x co-polymers(a) and AEMs(b)

Fig.5 Water uptake of p(St-co-VBC)-x AEMs

Fig.6 Ion exchange capacities of p(St-co-VBC)-x AEMs

Fig.7 Mechanical properties of p(St-co-VBS) AEMs

Fig.8 Temperature dependence of the hydroxyl conductivities of p(St-co-VBC)-x AEMs

Fig.9 Alkaline stability of p(St-co-VBC)-x AEMs

Table 1 Comparison of hydroxide conductivity with similar AEM materials

AEM material	Conductivity/(mS·cm^-1)	Ref.
AEMs containing mobile ion shuttles	189.0(90 ℃)	[20]
Imidazolium-functionalized poly(ether sulfone)	78.5(80 ℃)	[21]
Poly(2,6-dimethyl-1,4-phenyleneoxide) containing1,2,4,5-tetramethylimidazolium	60.0(80 ℃)	[22]
Imidazolium-poly(2,6-dimethyl-1,4-phenyleneoxide) blended with polyvinylalcohol	49.1(80 ℃)	[23]
Poly(styrene-co-vinylbenzylmethylimidazolium)	17.1(80 ℃)	[24]
p(St-co-VBC)-3 AEMs	68.4(80 ℃)	This work

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新型双功能交联型阴离子交换膜的制备与性能

Synthesis and Performance of Novel Bis-functional Cross-linked Anion Exchange Membranes^†

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新型双功能交联型阴离子交换膜的制备与性能

Synthesis and Performance of Novel Bis-functional Cross-linked Anion Exchange Membranes†

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Synthesis and Performance of Novel Bis-functional Cross-linked Anion Exchange Membranes^†