“点击化学”离子化聚砜对磺化聚醚醚酮/聚砜共混膜性能的影响研究

陈琛; 党杰; 李小雨; 许召赞; 李恩泽; 成怀刚; 程芳琴

doi:10.11777/j.issn1000-3304.2023.23135

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“点击化学”离子化聚砜对磺化聚醚醚酮/聚砜共混膜性能的影响研究

研究论文 | 更新时间：2024-03-28

- “点击化学”离子化聚砜对磺化聚醚醚酮/聚砜共混膜性能的影响研究
- Effect of Ionized Polysulfone via Click Chemistry on the Property and Separation Performance of Sulfonated Polyether Ether Ketone/Polysulfone Blend Membrane
- 高分子学报 2023年54卷第12期页码：1899-1910
- 作者机构：
  
  山西大学资源与环境工程研究所 CO2减排与资源化利用教育部工程研究中心太原 030006
- 作者简介：
  
  E-mail: zhaozanxu@sxu.edu.cn
  cfangqin@sxu.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 ┣21908136);U20A20149┫
- DOI：10.11777/j.issn1000-3304.2023.23135
  中图分类号：
- 纸质出版日期：2023-12-20，
  
  网络出版日期：2023-09-08，
  
  收稿日期：2023-05-17，
  
  录用日期：2023-07-04
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陈琛,党杰,李小雨等.“点击化学”离子化聚砜对磺化聚醚醚酮/聚砜共混膜性能的影响研究[J].高分子学报,2023,54(12):1899-1910.

Chen Chen,Dang Jie,Li Xiao-yu,et al.Effect of Ionized Polysulfone via Click Chemistry on the Property and Separation Performance of Sulfonated Polyether Ether Ketone/Polysulfone Blend Membrane[J].Acta Polymerica Sinica,2023,54(12):1899-1910.
陈琛,党杰,李小雨等.“点击化学”离子化聚砜对磺化聚醚醚酮/聚砜共混膜性能的影响研究[J].高分子学报,2023,54(12):1899-1910. DOI： 10.11777/j.issn1000-3304.2023.23135.

Chen Chen,Dang Jie,Li Xiao-yu,et al.Effect of Ionized Polysulfone via Click Chemistry on the Property and Separation Performance of Sulfonated Polyether Ether Ketone/Polysulfone Blend Membrane[J].Acta Polymerica Sinica,2023,54(12):1899-1910. DOI： 10.11777/j.issn1000-3304.2023.23135.

摘要

为制备氢离子/二价金属离子渗透选择性优异的阳离子交换膜，探究功能基团(季铵基团、羧基)含量对膜性能的影响规律，采用“点击化学”反应，在聚砜(PSF)侧链接枝季铵基团和羧基获得离子化PSF，将其与磺化聚醚醚酮(SPEEK)共混制备阳离子交换膜，分别通过离子化PSF添加量、功能化度和侧链阴阳离子比例调控共混膜中季铵基团含量，探究其对膜性能的影响规律. 膜对氢离子和亚铁离子的渗透选择性随着离子化PSF含量和功能化度的增加均呈现先升高后降低的趋势，当离子化PSF的季铵与羧基比例为1:1时，共混膜的渗透选择性最佳. 季铵基团与磺酸基形成离子对有利于抑制膜溶胀，通过Donnan排斥和尺寸筛分效应提高阳离子交换膜的渗透选择性；但当季铵基团的含量超过一定值，离子簇的形成导致其在膜内分布不均，膜的渗透选择性有所降低. 羧基则通过形成氢键减小膜的氢离子渗透性降低幅度.

Abstract

In order to fabricate cation exchange membrane with good permselectivity of proton/divalent metal ions

the influence of functional group (quaternary ammonium group and carboxyl group) content on the membrane performance was investigated. The ionic polysulfone (PSF) with pendent quaternary ammonium group and carboxyl group was synthesized by "click chemistry" reaction and blended into sulfonated polyether ether ketone (SPEEK). The content of quaternary ammonium group in the blend membrane was adjusted by the amount of ionized PSF

the functionalization degree of PSF and the ratio of quaternary ammonium group to carboxyl group

respectively. With the increase of ionized PSF content

the water uptake rate

swelling degree and proton flux of blend membrane gradually decreased

while the membrane surface resistance increased. The permselectivity of blend membrane for hydrogen and ferrous ions increased first and then decreased with the increase of ionized PSF content. When the ionized PSF content was 40%

the highest permselectivity of blend membrane (312.86) was obtained

which was 38 times that of SPEEK. Its proton flux (3.51 mmol·m

-2

·s

-1

) decreased to 38% that of SPEEK membrane (9.23 mmol·m

-2

·s

-1

). The permselectivity of blend membrane increased first and then decreased with the increasing functionalization degree of ionized PSF. The permselectivity of PSF-X10Y10 membrane was 12 times and 3.5 times that of PSF-X6Y6 and PSF-X15Y15 membranes

respectively. The permselectivity of PSF-X10Y10 membrane was 4 times and twice that of PSF-X7Y13 and PSF-X13Y7 membranes

respectively. The formation of ion pairs between quaternary ammonium group and sulfonic acid group was beneficial to inhibit membrane swelling

and the permselectivity of membrane was improved

via

Donnan repulsion and size-sieving effect. However

when the content of quaternary ammonium group exceeds a certain value

the formation of ion clusters leads to the uneven distribution of functional groups in the membrane

and the permselectivity of the membrane decreases. The reduction extent of proton flux could be decreased by increased carboxyl group content

via

the formation of hydrogen bond.

关键词

阳离子交换膜渗透选择性点击化学离子簇

Keywords

Cation exchange membranePermselectivityClick chemistryIon cluster

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