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Emulsion polymerization and application of perfluorosulfonic
acid polymers in confined space

Authors： XU Kangwei1, ZHANG Anyang1, XUE Shuai2, WANG Li2, CHEN Yue2, ZOU Yecheng2, WEI Gang2, PEI Supeng3, LIU Feng1,2, ZHANG Yongming1,2

Units： 1. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China; 2. State Key Laboratory of Fluorinated Functional Membrane Materials, Zibo 256401, China; 3. School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China

KeyWords： perfluorinated proton exchange membrane; perfluorosulfonic acid polymer; free radical polymerization; chlor-alkali electrolysis cell; fuel cell

ClassificationCode：TQ325.3

year,volume(issue):pagination： 2025,45(2):12-19

Abstract：

Perfluorosulfonic acid (PFSA) polymers are essential in fuel cells and the chlor-alkali industry, but traditional synthesis methods are limited in controlling molecular weight and sulfonic acid group distribution. This study introduces a novel approach called “confined space single-active-site radical polymerization”. By designing and synthesizing ammonium perfluoropolyether carboxylate (PFPE-NH4) as an emulsifier for emulsion polymerization, efficient and controllable polymerization of tetrafluoroethylene (TFE) and perfluorovinyl ether sulfonyl fluoride (PSVE) monomers was achieved. Various physical and chemical characterization techniques were used to analyze the polymerization dispersion state and polymer properties. The results showed that this new method significantly enhanced the molecular weight and distribution of PFSA polymers (Mn=272 000, Mw/Mn=1.65), with ion exchange capacity tunable through monomer composition ratios. Additionally, the macromolecular polymers markedly improved the material’s tensile strength (34.6 MPa). Furthermore, the prepared ion exchange membranes exhibited exceptional performance in fuel cells and chlor-alkali electrolysis, including high power density (1.59 W/cm2), low open circuit voltage (OCV) decay rate (0.16 mV/h), and minimal electrolyzer voltage increase rate (0.91 mV/month). This study offers a new pathway for the preparation of high-quality PFSA polymers.

Funds：

国家重点研发计划（2022YFB3808900， 2022YFB3808902）

AuthorIntro：

徐康伟（1998-），男，山东莱阳人，博士研究生，主要研究方向为含氟功能材料合成及应用

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