Gemini型碱性离子液体的制备及其在吡啶功能化PVA阴离子膜中的应用

王一夫; 万贺廷; 王丹; 王吉林; 王璐璐; 封瑞江

doi:10.11777/j.issn1000-3304.2017.17150

您当前的位置：

首页 >

文章列表页 >

Gemini型碱性离子液体的制备及其在吡啶功能化PVA阴离子膜中的应用

研究论文 | 更新时间：2021-01-26

- Gemini型碱性离子液体的制备及其在吡啶功能化PVA阴离子膜中的应用
- Synthesis of Gemini Basic Ionic Liquids and Its Application for Anion Exchange Membranes Based on Pyridine Functionalized Poly(vinyl alcohol)
- 高分子学报 2018年第4期页码：541-552
- 作者机构：
  
  辽宁石油化工大学化学化工与环境学部抚顺 113001
- 作者简介：
  
  王吉林, E-mail: wangjilin1978@163.com Ji-lin Wang, E-mail: wangjilin1978@163.com
- 基金信息：
  
  辽宁省科技厅博士启动项目(20141126);辽宁省教育厅科学研究一般项目(L2013153);抚顺市科学技术发展资金计划项目(20141115)
- DOI：10.11777/j.issn1000-3304.2017.17150
  中图分类号：
- 纸质出版日期：2018-4-20，
  
  收稿日期：2017-6-5，
  
  修回日期：2017-7-4，
扫描看全文
王一夫, 万贺廷, 王丹, 王吉林, 王璐璐, 封瑞江. Gemini型碱性离子液体的制备及其在吡啶功能化PVA阴离子膜中的应用[J]. 高分子学报, 2018,(4):541-552.

Yi-fu Wang, He-ting Wan, Dan Wang, Ji-lin Wang, Lu-lu Wang, Rui-jiang Feng. Synthesis of Gemini Basic Ionic Liquids and Its Application for Anion Exchange Membranes Based on Pyridine Functionalized Poly(vinyl alcohol)[J]. Acta Polymerica Sinica, 2018,(4):541-552.
王一夫, 万贺廷, 王丹, 王吉林, 王璐璐, 封瑞江. Gemini型碱性离子液体的制备及其在吡啶功能化PVA阴离子膜中的应用[J]. 高分子学报, 2018,(4):541-552. DOI： 10.11777/j.issn1000-3304.2017.17150.

Yi-fu Wang, He-ting Wan, Dan Wang, Ji-lin Wang, Lu-lu Wang, Rui-jiang Feng. Synthesis of Gemini Basic Ionic Liquids and Its Application for Anion Exchange Membranes Based on Pyridine Functionalized Poly(vinyl alcohol)[J]. Acta Polymerica Sinica, 2018,(4):541-552. DOI： 10.11777/j.issn1000-3304.2017.17150.

摘要

通过两步法合成具有Gemini结构的碱性十二烷基吗啉离子液体（[Nbmd]OH）.并将制得的离子液体引入吡啶功能化聚乙烯醇（PVA-FP）为基质的阴离子交换膜制备过程中，通过流延法制备PVA-FP/[Nbmd]

OH复合膜.借助傅里叶变换红外光谱（FTIR）、扫描电子显微镜（SEM）、X射线衍射（XRD）、交流阻抗（AC）、热重分析（TGA）及机械性能测试等对复合膜的结构及理化性能进行表征.结果表明，该系列复合膜形貌平整均一，吡啶基团的引入增强了PVA基质膜的热稳定性及耐碱稳定性.[Nbmd]OH离子液体的引入，在提供更多阳离子活性点位的同时，降低了复合膜结晶度，提高了电导率，改善了机械性能.其中，当质量比

（PVA）：

（[Nbmd]OH）=1：2.5时，复合膜的热分解温度较PVA膜提高75℃；70℃时电导率达到4.42×10

-2

S·cm

-1

；在80℃，6 mol/L KOH溶液中进行加速老化实验，浸泡400 h后电导率为初始电导率的1.6倍左右，表现出优异的耐碱稳定性；在30 ℃，3 mol/L甲醇溶液中甲醇透过率仅为Nafion

-117膜的2.5%~5%，表现出很好的阻醇性能.

Abstract

A new Gemini basic morpholine ionic liquid (IL

[Nbmd]OH) was synthesized with morphline

bromodecane and 1

4-dibromobutane

via

a two-step procedure. The structure of the new IL was characterized by

H-NMR and FTIR. A series of anion exchange membranes (PVA-FP/[Nbmd]OH) were prepared by casting method with pyridine functionalized poly(vinyl alcohol) as the polymer matrix. The PVA-FP/[Nbmd]

OH composite membranes were characterized in details by AC-impedance spectroscopy

Fourier transform infrared spectroscopy (FTIR)

X-ray diffraction (XRD)

scanning electron microscopy (SEM)

thermal gravimetric analysis (TGA) and tensile strength test. The results indicated that PVA-FP/[Nbmd]OH composite membranes have uniform morphology

and the introduction of pyridine groups enhance the thermal stability and alkali resistance of PVA matrix

due to the formation of the hyper conjugation structure between

bond (C-H bond in methyl group) and

-bond conjugated region (pyridine group)

therefore enlarging the conjugated region

decreasing the positive charge density of the cations. Meanwhile

[Nbmd]OH ionic liquid not only provided more cationic active sites but also reduced the crystalline of the composite membranes

resulting in an increase of OH

conductivity and an improvement of the mechanical properties. When the weight ratio of[Nbmd]OH to PVA was 2.5

the thermal decomposition temperature of the composite membrane was 75℃ higher than that of the pristine PVA membrane; the maximum OH

conductivity was found at about 4.42×10

-2

S·cm

-1

at 70℃; no obvious decrease in OH

conductivity was observed for the composite membrane after immersing in 6 mol/L KOH solution at 80℃. On the contrary

the OH

conductivity was improved to 1.6 times of the initial OH

conductivity after 400 h immersion time

showing an excellent alkali resistance stability. In addition

the methanol permeability of the composite membrane determined using 3 mol/L methanol solution at 30℃ was only about 2.5%-5% of the commercial Nafion

-117 membrane under the same test conditions

indicating a promising potential use in alkaline direct methanol fuel cells.

关键词

阴离子交换膜聚乙烯醇离子液体耐碱稳定性甲醇透过率

Keywords

Anion exchange membranePoly(vinyl alcohol)Ionic liquidAlkali resistance stabilityMethanol permeability

references

J R Varcoe , R C Slade , H Y E Lam . Chem Commun , 2006 . 3 ( 13 ): 1428 - 1429 . http://www.ncbi.nlm.nih.gov/pubmed/16550289.

S Kim , I Hong . J Ind Eng Chem , 2010 . 16 901 DOI:10.1016/j.jiec.2010.05.017http://doi.org/10.1016/j.jiec.2010.05.017.

R M A Abdel , H R M Abdel , M W Khalia . J Power Sources , 2004 . 134 160 - 169 . DOI:10.1016/j.jpowsour.2004.02.034http://doi.org/10.1016/j.jpowsour.2004.02.034.

O Savadogo . J Power Sources , 2004 . 127 135 - 161 . DOI:10.1016/j.jpowsour.2003.09.043http://doi.org/10.1016/j.jpowsour.2003.09.043.

L Pasquini , M L D Vona , P Knauth . New J Chem , 2016 . 40 ( 4 ): 3671 - 3676 . DOI:10.1039/C5NJ03212Ahttp://doi.org/10.1039/C5NJ03212A.

E N Komkova , D F Stamatialis , H Strathmann . J Membr Sci , 2004 . 244 ( 1-2 ): 25 - 34 . DOI:10.1016/j.memsci.2004.06.026http://doi.org/10.1016/j.memsci.2004.06.026.

Lingling Liu , Lei Ding , Li Xu , Jinin Qiao , Jiawei Shen . Acta Phys Chim Sin , 2011 . 27 ( 11 ): 2665 - 2670 . DOI:10.3866/PKU.WHXB20111106http://doi.org/10.3866/PKU.WHXB20111106.

刘玲玲 , 丁蕾 , 徐莉 , 乔锦丽 , 盛嘉伟 . 物理化学学报 , 2011 . 27 ( 11 ): 2665 - 2670 . DOI:10.3866/PKU.WHXB20111106http://doi.org/10.3866/PKU.WHXB20111106.

F Zhang , H Zhang , C Qu . J Mater Chem , 2011 . 21 ( 34 ): 12744 - 12752 . DOI:10.1039/c1jm10656bhttp://doi.org/10.1039/c1jm10656b.

W Li , J Fang , M Lv . J Mater Chem , 2011 . 21 ( 30 ): 11340 - 11346 . DOI:10.1039/c1jm11093dhttp://doi.org/10.1039/c1jm11093d.

J S Leea , T Nohiraa , R Hagiwara . J Power Sources , 2007 . 171 ( 171 ): 535 - 539 . https://es.scribd.com/document/155091968/Clinical-Chest-Ultrasound.

X Zhu , B Wang , H Wang . Polym Bull , 2010 . 65 ( 7 ): 719 - 730 . DOI:10.1007/s00289-010-0321-yhttp://doi.org/10.1007/s00289-010-0321-y.

S Yi , F Zhang , L Wei . J Membr Sci , 2011 . 366 ( 1-2 ): 349 - 355 . DOI:10.1016/j.memsci.2010.10.031http://doi.org/10.1016/j.memsci.2010.10.031.

Guoyu Liu , Daming Gu , Haiyan Liu , Wei Ding . Acta Chimica Sinica , 2012 . 70 ( 1 ): 6 - 14 . http://sioc-journal.cn/Jwk_hxxb/CN/abstract/abstract333564.shtml.

刘国宇 , 顾大明 , 刘海燕 , 丁伟 . 化学学报 , 2012 . 70 ( 1 ): 6 - 14 . http://sioc-journal.cn/Jwk_hxxb/CN/abstract/abstract333564.shtml.

M S Ewa , C Malgorzata , S Stefan , S Piotr . Curr Org Chem , 2011 . 15 1974 - 1991 . DOI:10.2174/138527211795703630http://doi.org/10.2174/138527211795703630.

G Yu , S Yan , F Zhou . Tribol Lett , 2007 . 25 ( 3 ): 197 - 205 . DOI:10.1007/s11249-006-9167-8http://doi.org/10.1007/s11249-006-9167-8.

L L Wang , Y Zhang , F Zhang . Energ Source Part A , 2016 . 38 ( 18 ): 2770 - 2776 . DOI:10.1080/15567036.2014.968746http://doi.org/10.1080/15567036.2014.968746.

T Sata , K Kawamura , K Matsusaki . J Membr Sci , 2001 . 181 ( 2 ): 167 - 178 . DOI:10.1016/S0376-7388(00)00507-Xhttp://doi.org/10.1016/S0376-7388(00)00507-X.

J Qiao , T Hamaya , T Okada . J Mater Chem , 2005 . 15 ( 15 ): 4414 - 4423.

Limei Wang , Liyan Dou , Peng Xin . Chem J Chinese U , 2016 . 37 ( 7 ): 1408 - 1414 . http://www.cjcu.jlu.edu.cn/CN/10.7503/cjcu20150983.

汪丽梅 , 窦立岩 , 辛鹏 . 高等学校化学学报 , 2016 . 37 ( 7 ): 1408 - 1414 . http://www.cjcu.jlu.edu.cn/CN/10.7503/cjcu20150983.

J ChoiY , J M Park , K H Yeon . J Membr Sci , 2005 . 250 ( 1-2 ): 295 - 304 . DOI:10.1016/j.memsci.2004.10.034http://doi.org/10.1016/j.memsci.2004.10.034.

T Zhou , J Zhang , J Qiao . J Power Sources , 2012 . 227 ( 4 ): 291 - 299 . http://www.sciencedirect.com/science/article/pii/S0378775312017156.

J Qiao , H A Takeo , T Okada . Chem Mater , 2005 . 17 ( 9 ): 2413 - 2421 . DOI:10.1021/cm048260thttp://doi.org/10.1021/cm048260t.

J Liang , Y Huang , L Zhang . Adv Funct Mater , 2010 . 19 ( 14 ): 2297 - 2302 . https://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1521-4095.

X Yang , L Li , S Shang . Polymer , 2010 . 51 ( 15 ): 3431 - 3435 . DOI:10.1016/j.polymer.2010.05.034http://doi.org/10.1016/j.polymer.2010.05.034.

X Zhu , B Wang , H Wang . Polym Bull , 2010 . 65 ( 7 ): 719 - 730 . DOI:10.1007/s00289-010-0321-yhttp://doi.org/10.1007/s00289-010-0321-y.

H J Salavagione , G Martínez , M A Gómez . J Mater Chem , 2009 . 19 ( 28 ): 5027 - 5032 . DOI:10.1039/b904232fhttp://doi.org/10.1039/b904232f.

Y S Ye , M Y Cheng , X L Xie . J Power Sources , 2013 . 239 ( 239 ): 424 - 432 . http://www.sciencedirect.com/science/article/pii/S0378775313004011.

Jing Fu , Rui Lin , Hong Lv , Xiaolei Wang , Jianxin Ma , Jinli Qiao . Acta Phys Chim Sin , 2010 . 26 ( 10 ): 2653 - 2658 . DOI:10.3866/PKU.WHXB20100918http://doi.org/10.3866/PKU.WHXB20100918.

傅婧 , 林瑞 , 吕洪 , 王晓蕾 , 马建新 , 乔锦丽 . 物理化学学报 , 2010 . 26 ( 10 ): 2653 - 2658 . DOI:10.3866/PKU.WHXB20100918http://doi.org/10.3866/PKU.WHXB20100918.

D S Kim , H B Park , W R Ji . Solid State Ionics , 2005 . 176 ( 1-2 ): 117 - 126 . DOI:10.1016/j.ssi.2004.07.011http://doi.org/10.1016/j.ssi.2004.07.011.

L L Wang , J L Wang , R J Feng . J Fuel Chem Technol , 2015 . 43 ( 1 ): 59 - 64.

Y Xiong , J Fang , Q H Zeng . J Membr Sci , 2007 . 311 ( 1 ): 319 - 325 . http://chem.xmu.edu.cn/kydw_ktz/qlliu/index.html.

Y Xiong , Q L Liu , Q G Zhang . J Power Sources , 2008 . 183 ( 2 ): 447 - 453 . DOI:10.1016/j.jpowsour.2008.06.004http://doi.org/10.1016/j.jpowsour.2008.06.004.

Q H Zeng , Q L Liu , I Broadwell . J Membr Sci , 2010 . 349 ( 1-2 ): 237 - 243 . DOI:10.1016/j.memsci.2009.11.051http://doi.org/10.1016/j.memsci.2009.11.051.

M C Zhou , L H Zhu . Instrumental Analysis , : Wuhan Huazhong University of Science & Technology Press , 2008 . 114 - 115.

G U Liang , Z Sun , X U Dan . J Funct Polym , 2016 . 29 ( 2 ): 153 - 162 . http://www.ntu.edu.sg/home/hzhang.

B Lin , H Dong , Y Li . Chem Mater , 2013 . 25 ( 9 ): 1858 - 1867 . DOI:10.1021/cm400468uhttp://doi.org/10.1021/cm400468u.

F Gu , H Dong , Y Li . Macromolecules , 2015 . 47 ( 1 ): 208 - 216 . http://pubs.acs.org/doi/abs/10.1021/ma402334t.

J Qiao , J Fu , R Lin . Polymer , 2010 . 51 ( 21 ): 4850 - 4859 . DOI:10.1016/j.polymer.2010.08.018http://doi.org/10.1016/j.polymer.2010.08.018.

更多指标>

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

锂内盐两性离子聚合物电解质的制备与电化学性能研究

双重热响应离子凝胶的构筑及相行为研究

基于静电纺丝的类海绵体材料用于溶菌酶的吸附行为

局部密集交联含氟聚芳醚阴离子交换膜的制备与性能

相变气凝胶的设计合成及其微环境调控性能研究