Ether-free Sulfonated Polyarylene-Based Proton Exchange Membranes by Superacid-catalyzed Friedel-Crafts Reaction

Zi-jun Huang; Zhi Long; Ce-neng Chen; Ke Xu; Bin-bin Qian; Yan-rong Ren; Tao Ding; Xiao-min Fang

doi:10.11777/j.issn1000-3304.2024.24175

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Ether-free Sulfonated Polyarylene-Based Proton Exchange Membranes by Superacid-catalyzed Friedel-Crafts Reaction

Research Article | 更新时间：2025-01-10

- Ether-free Sulfonated Polyarylene-Based Proton Exchange Membranes by Superacid-catalyzed Friedel-Crafts Reaction
- Acta Polymerica Sinica Vol. 55, Issue 12, Pages: 1730-1741(2024)
- 作者机构：
  
  1.河南大学化学与分子科学学院开封 475001
  2.中国科学院深圳先进技术研究院深圳 518055
  3.深圳理工大学材料科学与能源工程学院深圳 518000
- 作者简介：
  
  Zhi Long, E-mail: z.long@siat.ac.cn
  Ke Xu, E-mail: ke.xu@siat.ac.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2024.24175
  CLC：
- CSTR：32057.14.GFZXB.2024.7283
- Published：20 December 2024，
  
  Published Online：24 October 2024，
  
  Received：21 June 2024，
  
  Accepted：2024-07-19
- 稿件说明：
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黄梓俊, 龙志, 陈策能, 徐珂, 钱彬彬, 任艳蓉, 丁涛, 房晓敏. 超强酸催化Friedel-Crafts反应制备无醚磺化聚芳基质子交换膜. 高分子学报, 2024, 55(12), 1730-1741

Huang, Z. J.; Long, Z.; Chen, C. N.; Xu, K.; Qian, B. B.; Ren, Y. R.; Ding, T.; Fang, X. M. Ether-free sulfonated polyarylene-based proton exchange membranes by superacid-catalyzed friedel-crafts reaction. Acta Polymerica Sinica, 2024, 55(12), 1730-1741
黄梓俊, 龙志, 陈策能, 徐珂, 钱彬彬, 任艳蓉, 丁涛, 房晓敏. 超强酸催化Friedel-Crafts反应制备无醚磺化聚芳基质子交换膜. 高分子学报, 2024, 55(12), 1730-1741 DOI： 10.11777/j.issn1000-3304.2024.24175. CSTR： 32057.14.GFZXB.2024.7283.

Huang, Z. J.; Long, Z.; Chen, C. N.; Xu, K.; Qian, B. B.; Ren, Y. R.; Ding, T.; Fang, X. M. Ether-free sulfonated polyarylene-based proton exchange membranes by superacid-catalyzed friedel-crafts reaction. Acta Polymerica Sinica, 2024, 55(12), 1730-1741 DOI： 10.11777/j.issn1000-3304.2024.24175. CSTR： 32057.14.GFZXB.2024.7283.

摘要

通过三氟甲磺酸催化Friedel-Crafts反应，合成了含有三氟异亚丙基的无醚聚芳前驱体聚合物. 考察了不同芳基单体、电子云密度和空间位阻等因素对前驱体聚合物分子量的影响，并优化反应条件，实现了前驱体的合成. 特别是，以联苄和三氟丙酮为原料合成的前驱体聚合物PAAF，展现出了高分子量(

=201 kDa，

=63 kDa)特性；随后，经氯磺酸三甲基硅烷基酯后磺化制备了sPAAF，其不仅保持了高分子量(

=201 kDa，

=63 kDa)，还具备了高离子交换容量(2.40 mmol/g). 在80 ℃完全水合状态下，质子电导率最高可达102 mS/cm，热分解温度为258 ℃，化学稳定性良好，在芬顿测试后质量衰减率仅为11%，表明该系列材料具有良好的化学稳定性. 本研究旨在通过引入不同的亚苯基结构和功能基团，深入探讨聚合物结构与膜性能之间的构效关系，为开发低成本、高性能的无醚聚苯基质子交换膜材料奠定基础.

Abstract

Proton exchange membrane (PEM) is one of the key components of PEM fuel cells. Sulfonated poly(arylenen ether)‍-based PEMs have gained much more attention due to easy synthesis and excellent mechanical and thermal properties. However

these PEMs containing ether bonds

which are vulnerable to free radical

show poor oxidative stability. Ether-free polyarylene-based polymer has become the most promising one

giving that no heteroatom is contained on the backbone. Up to now

it has been synthesized only by metal-catalyzed polymerization

Diels-Alder polymerization and superacid-catalyzed polymerization. Superacid-catalyzed polymerization is an easy approach to providing the polymer with pendent alkyl sulfonic acid rather than aryl sulfonic acid. Herein

ether-free polyarylene-based precursors containing trifluoroisopropylidene were successfully synthesized

via

the trifluoromethanesulfonic acid-catalyzed Friedel-Crafts reaction and then post-sulfonated to obtain ether-free polyarylene-based PEM containing arylene sulfonic acid and trifluoroisopropylidene on the backbone. The effects of the substituents

electron cloud density

and steric hindrance on the molecular weight of the precursor polymers were investigated. The arylene-based monomer with high electron cloud density provided high reaction activity and molecular weight (

200 kDa)

such as fluorene and 9

9-diphenylfluorene

but those after post sulfonation cannot provide flexible membranes due to the rigidity of mainchain. Considering to the balance between electron cloud density and rigidity

a precursor polymer consisting of trifluoroisopropylidene and bibenzyl (PAAF) demonstrated a high molecular weight of 201 kDa and provided flexible membrane after post-sulfonation. Giving that PAAF was not dissolved in concentrated sulfonic acid and easily precipitated from dichloromethane after dropping chlorosulfonic acid

those common post-sulfonation was useless. Chlorosulfonic a

cid trimethylsilyl ester was used to obtain sulfonated poly(arylene alkylene)‍-based polymers (sPAAF). sPAAF with various ion exchange capabilities of 1.24-2.40 mmol/g was prepared

via

control concentration of sulfonated solvent. At 80 ℃ and in a fully hydrated state

its proton conductivity reached up to 102 mS/cm

with a high thermal decomposition temperature of 256 ℃ and good chemical stability

showing a degradation rate between 10% and 20% after Fenton's test. This study aims to lay a theoretical foundation for the development of low-cost

high-performance ether-free sulfonated polyarylene-based PEMs by exploring the relationship between the structure and bulk properties.

关键词

聚合物合成质子交换膜无醚聚苯磺酸功能化

Keywords

Polymer synthesisProton exchange membraneEther-free polyaryleneSulfonic acid functionalization

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Related Institution

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南京理工大学环境与生物工程学院

Department of Nonwoven materials and Engineering, College of Textile, Tianjin Polytechnic University

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