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2025 , Vol. 83 >Issue 1: 36 - 44

DOI: https://doi.org/10.6023/A24120365

研究论文

新型氟醚甜菜碱型表面活性剂的合成及性能表征

  • 李俊毅 ,
  • 黄美薇 ,
  • 张运文 ,
  • 邹灿 ,
  • 刘超 ,
  • 郭勇
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  • a 上海应用技术大学 化学与环境工程学院 上海 201418
    b 中国科学院上海有机化学研究所 先进氟氮材料全国重点实验室 上海 200032
    c 三明市海斯福化工有限责任公司 三明 365200

收稿日期: 2024-12-05

  网络出版日期: 2025-01-07

基金资助

国家重点研发计划(2023YFC39005205); 福建省科学技术厅(2023T3066); 国家自然科学基金(22471172)

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Synthesis and Characterization of Novel Betaine-type Fluoroether Surfactants

  • Junyi Li ,
  • Meiwei Huang ,
  • Yunwen Zhang ,
  • Can Zou ,
  • Chao Liu ,
  • Yong Guo
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  • a School of Chemical and Environment Engineering, Shanghai Institute of Technology, Shanghai 201418
    b State Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
    c Sanming Hexafluo Chemicals Company, Ltd., Sanming, Fujian 365200
*E-mail: ;
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Received date: 2024-12-05

  Online published: 2025-01-07

Supported by

National Key Research and Development Program of China(2023YFC39005205); Science and Technology Department of Fujian Province(2023T3066); National Natural Science Foundation of China(22471172)

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摘要

甜菜碱型氟表面活性剂结合了两性表面活性剂和氟表面活性剂的优势, 因此呈现出优越的性能, 被应用于诸多领域. 代表性化合物是PFOS-AB(全氟辛烷磺酸甜菜碱衍生物). 2009年, 全氟辛烷磺酸(PFOS)及其衍生物因负面的环境效应被《斯德哥尔摩公约》限制生产和使用. 虽然替代品层出不穷, 但目前为止市场上还未出现性能超越PFOS-AB, 同时环境友好的产品. 本工作合成了4个氟醚甜菜碱型表面活性剂, 引入可降解含氟链段C361 (R1=CF3CF2CF2OCHFCF2SCH2CH2-)和X2 (R2=CF3OCF2OCF2CF2OCHFCF2SCH2CH2-). 测试了它们在低浓度下的表面活性性能、铺展性能、泡沫性能以及润湿性能. 结果显示, 化合物D361-B(含两条R1链的氟醚烷基甜菜碱衍生物)的表面活性性能超越了PFOS-AB; X2-B(含一条R2链的氟醚烷基甜菜碱衍生物)和DX2-B(含两条R2链的氟醚烷基甜菜碱衍生物)的表面活性性能超越了现有替代品6:2 FTAB(全氟己基乙基磺酸甜菜碱衍生物). 化合物X2-B有较好的铺展性能和综合泡沫性能. 本工作设计的新型氟醚甜菜碱型表面活性剂, 通过双疏水链结构, 提升了表面活性; 同时引入可降解含氟链段, 提升了环境友好性, 有望成为新一代PFOS替代品.

关键词： 氟醚表面活性剂; 甜菜碱型; 表面张力; 临界胶束浓度; PFOS替代品

本文引用格式

李俊毅 , 黄美薇 , 张运文 , 邹灿 , 刘超 , 郭勇 . 新型氟醚甜菜碱型表面活性剂的合成及性能表征[J]. 化学学报, 2025 , 83(1) : 36 -44 . DOI: 10.6023/A24120365

Abstract

Betaine-type fluorinated surfactants have some superior properties, which make them have a wide application prospect. These surfactants combine the properties of amphoteric and fluorinated surfactants. Among them, PFOS-AB (betaine derived from perfluorooctane sulfonic acid) is the most effective surfactant due to its high surface activity. However, PFOS (perfluorooctane sulfonic acid) and its derivatives have been identified as having potential adverse effects on the environment and human health. As a result, they are severely restricted by the Stockholm Convention. Manufacturers and users of PFOS are under increasing pressure to switch to environmentally friendly alternatives. Unfortunately, this remains a challenging problem. In this study, we focused on novel betaine-type fluoroether surfactants, which have one or a dual chain structure composed of biodegradable hydrophobic chains. In the synthesis of betaine fluorinated surfactants, the fluorinated chains of C361 (R1=CF3CF2CF2OCHFCF2SCH2CH2-) and X2 (R2=CF3OCF2OCF2CF2OCHFCF2SCH2CH2-) were selected. These new fluorinated surfactants are expected to be safer, more biodegradable and high-performance. Additionally, the surface tension and interfacial tension were measured; the critical micelle concentration (cmc), the limiting molecular areas (Amin) and the fluorine content were obtained; and the foam properties as well as the wettability on polytetrafluoroethylene (PTFE) and glass were also tested. By comparing the traditional PFOS-AB and the currently popular 6:2 FTAB (betaine derived from perfluorohexyl ethyl sulfonic acid), we found that the surface activity of D361-B (Betaine derived from fluoroether alkyl containing two R1 chains) is better than that of PFOS-AB, and the surface activity of X2-B (Betaine derived from fluoroether alkyl containing one R2 chains) and DX2-B (Betaine derived from fluoroether alkyl containing two R2 chains) is better than that of 6:2 FTAB. In particular, the surface tension of D361-B reached 16.8 and 21.1 mN•m−1 at low concentrations of 0.1 and 0.01 g•L−1, respectively, and its fluorine content was lower than that of similar products. The surface tension of X2-B is comparable to that of PFOS-AB, and the spreading and foam properties are also outstanding. In conclusion, this study provides guidance for the development of a new generation of sustainable surfactants with the potential to replace PFOS.

Key words： fluoroether surfactant; betaine-type; surface tension; critical micelle concentration; alternative for PFOS

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