Synthesis and Characterization of Gemini Cationic Fluoroether Surfactants
Received date: 2024-12-14
Online published: 2025-01-24
Supported by
National Key Research and Development Program of China(2023YFC39005205); Science and Technology Department of Fujian Province(2023T3066)
The gemini cationic surfactant is a type of surfactant that simultaneously connects at least two hydrophobic hydrocarbon chains and two polar head groups through one intermediate group. Multiple hydrophobic chain segments and hydrophilic groups act concurrently in the system, enabling more effective reduction of the surface tension within the system. However, within the research realm of alternatives to fluorinated surfactants, the potential of the gemini cationic surfactant structure as a substitute has received relatively little attention. In this study, we synthesized tertiary amines using CF3OCF(CF3)CF2OCF(CF3)- (C72), CF3(OCF2)3- (OC3), CF3(OCF2)4- (OC4) and C5F11- (C6) methyl esters in methanol solvent at room temperature. Subsequently, a series of gemini cationic surfactants were obtained through the quaternization of the tertiary amine with one benzylbromide and three dibromide compounds in acetonitrile solvent. The reaction conditions for most samples were mild. After purification, the purity of the samples could nearly reach 95%, which rendered the surface activity characterization results more accurate and persuasive. The sample named C72(Et)-o-phenyl-C72, which features diethyl substitution, requires the optimization of reaction conditions. Subsequent purification through column chromatography is necessary to obtain products of high purity. 1% (w), 0.1% (w), 0.01% (w) and 0.001% (w) solutions were prepared for each compound, and the surface tension was measured by the Wilhelmy plate method. The properties of the samples were compared, and the rule between the properties of fluorine-containing gemini cationic surfactants and the degree of incorporation of oxygen atoms on the hydrophobic chain, as well as their different isomers, was preliminarily explored. The results suggest that the characterization results of OC3 and OC4 series samples, of which hydrophobic chain segment featured repetitive -OCF2O- units, are the most favorable, and the sample properties are minimally affected by the structure. The sample surface activity of C72 series samples, whose hydrophobic chain segment contains only two oxygen atoms, are relatively low, while the sample characterization results of C6 samples, which has no oxygen atoms, are the least outstanding. The results manifest the uniqueness and feasibility of the fluoroether chain segment gemini cationic surfactants, and the structure has potential to serve as a substitute for long-chain fluorocarbon surfactants.
Sijing Wang , Yong Guo , Chengying Wu . Synthesis and Characterization of Gemini Cationic Fluoroether Surfactants[J]. Acta Chimica Sinica, 2025 , 83(2) : 126 -131 . DOI: 10.6023/A24120369
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