Synthesis and Characterization of Gemini Cationic Fluoroether Surfactants

doi:10.6023/A24120369

Abstract

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.

Key words: gemini cationic surfactant, fluorocarbon surfactant, fluoroether chain, surface tension, quaternization reaction

Cite this article

Sijing Wang, Yong Guo, Chengying Wu. Synthesis and Characterization of Gemini Cationic Fluoroether Surfactants[J]. Acta Chimica Sinica, 2025, 83(2): 126-131.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 6

References 25

[1]	Kissa, E. Fluorinated Surfactants and Repellents, Marcel Dekker Inc., New York, 2001, pp. 1-21.
[2]	Czajka, A.; Hazell, G.; Eastoe, J. Langmuir 2015, 31, 8205. doi: 10.1021/acs.langmuir.5b00336 pmid: 25797065
[3]	Krafft, M.-P.; Riess, J. G. Curr. Opin. Colloid Interface Sci. 2015, 20, 192.
[4]	Evich, M. G.; Davis, M. J. B.; McCord, J. P.; Acrey, B.; Awkerman, J. A.; Knappe, D. R. U.; Lindstrom, A. B.; Speth, T. F.; Tebes-Stevens, C.; Strynar, M. J.; Wang, Z.; Weber, E. J.; Henderson, W. M.; Washington, J. W. Science 2022, 375, eabg9065.
[5]	Wen, Z.-J.; Wei, Y.-J.; Zhang, Y.-F.; Zhang, Y.-F. Arch. Toxicol. 2023, 97, 1195.
[6]	Peritore, A.-F.; Gugliandolo, E.; Cuzzocrea, S.; Crupi, R.; Britti, D. Int. J. Mol. Sci. 2023, 24, 11707.
[7]	Qian, L.; Huang, M.; Guo, Y.; Chen, Q.-Y. Perfluoroalkyl Substances: Synthesis, Applications, Challenges and Regulations, Ed.: Améduri, B., The Royal Society of Chemistry, Cambridge, 2022, Chapter 5, pp. 146-165.
[8]	Dai, L.; Guo, Y.; Su, Z.; Huang, M.; Chen, Q.-Y.; Zhao, Z.-G.; Wu, C.; Su, Q.; Shen, Q. J. Fluorine Chem. 2021, 246, 109793.
[9]	Liao, C. Y.; Guo, S. W.; Huang, M. W.; Guo, Y.; Chen, Q. Y.; Liu, C.; Zhang, Y. W. Acta Chim. Sinica 2024, 82, 46 (in Chinese).
	(廖晨宇, 郭山巍, 黄美薇, 郭勇, 陈庆云, 刘超, 张运文, 化学学报, 2024, 82, 46.) doi: 10.6023/A23090430
[10]	Guo, S.; Guo, Y.; Huang, M.; Qian, L.; Su, Z.; Chen, Q.-Y.; Wu, C.; Liu, C. Langmuir 2023, 39, 14519.
[11]	Xu, Y.; Guo, Y.; Qian, L.; Su, Z.; Chen, Q.-Y.; Wang, J.; Jiang, L. Langmuir 2024, 40, 1316.
[12]	Munoz, G.; Liu, J.; Duy, V. S.; Sauve, S. Trends Anal. Chem‌‌. 2019, 23, 2214.
[13]	Lan, Y.; Nie, P.; Yuan, H.; Xu, H. Sci. Total Environ. 2024, 951, 175609.
[14]	Li, S.; Wu, L. Y.; Zeng, H. X.; Zhang, J.; Qin, S. J.; Liang, L.-X.; Andersson, J.; Meng, J.-W.; Chen, Q.-Z.; Lin, L.-Z.; Chou, W.-C.; Dong, G.-H.; Zeng, X.-W. Environ. Res‌‌. 2024, 248, 118305.
[15]	Qian, L.; Guo, Y.; Cao, W. Organo-Fluor. Ind. 2021, 04, 39 (in Chinese).
	(钱力波, 郭勇, 曹伟, 有机氟工业, 2021, 04, 39. )
[16]	Guo, H.; Sheng, N.; Guo, Y.; Wu, C.; Xie, W.; Dai, J. Environ. Pollut. 2021, 291, 118202.
[17]	Dunn, F.; Paquette, S. E.; Pennell, D. K.; Plavicki, S. J.; Manz, K. E. Aquat. Toxicol. 2024, 271, 106908.
[18]	Guo, H.; Wang, J.; Yao, J.; Sun, S.; Sheng, N.; Zhang, X.; Guo, X.; Guo, Y.; Sun, Y.; Dai, J. Environ. Sci. Technol. 2019, 53, 3929.
[19]	Wang, X.; Huang, M.; Su, Z.; Qian, L.; Guo, Y.; Chen, Q.-Y.; Wu, C.; lv, T.; Su, Q.; Shen, Q.; Ma, J. Chinese Chem. Lett. 2023, 34, 107961. doi: 10.1016/j.cclet.2022.107961
[20]	Bunton, C. A.; Robinson, L.; Schaak, J.; Stam, M. F. J. Org. Chem. 1971, 16, 36.
[21]	Menger, F. M.; Littau, C. A. J. Am. Chem. Soc. 1991, 113, 1451.
[22]	Du, F.; Guo, Y.; Huang, M.; Chen, Q.; Yang, H.; Xie, W.; Cao, W.; Wu, C.; Wang, M. J. Fluorine Chem. 2020, 239, 109632.
[23]	Coope, T.; Moloy, K.; Yake, A.; Petrov, V.; Taylor, C.; Hung, M.; Peng, S. J. Fluorine Chem. 2014, 161, 41.
[24]	Nessim, M. I.; Osman, M. M.; Ismail, D. A. J. Disper. Sci. Technol. 2017, 39, 1047.
[25]	Xu, Y.; Qian, L. B.; Guo, Y.; Chen, Q. Y. Organo-Fluor. Ind. 2023, 01, 57 (in Chinese).
	(许圆, 钱力波, 郭勇, 陈庆云, 有机氟工业, 2023, 01, 57.)

Compound	Surface tension/(mN•m⁻¹)
Compound	1% (w)	0.1% (w)	0.01% (w)	0.001% (w)
C72(Me)-s-phenyl	—	30.8	53.3	63.7
C72(Me)-o-phenyl-C72	—	18.6	28.0	43.3
C72(Me)-m-phenyl-C72	—	21.1	32.3	52.2
C72(Me)-p-phenyl-C72	—	—	37.4	56.6
C72(Et)-s-phenyl	—	29.6	49.1	66.3
C72(Et)-o-phenyl-C72	—	16.8	21.5	45.6
C72(Et)-m-phenyl-C72	—	20.5	31.8	51.4
C72(Et)-p-phenyl-C72	17.8	21.3	32.2	55.6
OC3-s-phenyl	20.3	18.5	55.9	60.4
OC3-o-phenyl-OC3	22.4	22.6	54.0	66.5
OC3-m-phenyl-OC3	21.6	24.5	58.9	64.0
OC3-p-phenyl-OC3	24.1	24.8	53.0	63.7
OC4-s-phenyl	18.9	17.2	23.8	66.0
OC4-o-phenyl-OC4	17.6	18.1	20.6	53.5
OC4-m-phenyl-OC4	18.9	18.7	21.4	56.5
OC4-p-phenyl-OC4	20.2	18.8	24.1	58.2
C6-s-phenyl	22.3	47.3	63.9	70.8
C6-o-phenyl-C6	19.4	23.2	48.9	66.0
C6-m-phenyl-C6	22.2	28.8	61.4	70.6
C6-p-phenyl-C6	—	39.7	66.2	71.2

Compound	Surface tension/(mN•m⁻¹)
Compound	1% (w)	0.1% (w)	0.01% (w)	0.001% (w)
C72(Me)-s-phenyl	—	30.8	53.3	63.7
C72(Me)-o-phenyl-C72	—	18.6	28.0	43.3
C72(Me)-m-phenyl-C72	—	21.1	32.3	52.2
C72(Me)-p-phenyl-C72	—	—	37.4	56.6
C72(Et)-s-phenyl	—	29.6	49.1	66.3
C72(Et)-o-phenyl-C72	—	16.8	21.5	45.6
C72(Et)-m-phenyl-C72	—	20.5	31.8	51.4
C72(Et)-p-phenyl-C72	17.8	21.3	32.2	55.6
OC3-s-phenyl	20.3	18.5	55.9	60.4
OC3-o-phenyl-OC3	22.4	22.6	54.0	66.5
OC3-m-phenyl-OC3	21.6	24.5	58.9	64.0
OC3-p-phenyl-OC3	24.1	24.8	53.0	63.7
OC4-s-phenyl	18.9	17.2	23.8	66.0
OC4-o-phenyl-OC4	17.6	18.1	20.6	53.5
OC4-m-phenyl-OC4	18.9	18.7	21.4	56.5
OC4-p-phenyl-OC4	20.2	18.8	24.1	58.2
C6-s-phenyl	22.3	47.3	63.9	70.8
C6-o-phenyl-C6	19.4	23.2	48.9	66.0
C6-m-phenyl-C6	22.2	28.8	61.4	70.6
C6-p-phenyl-C6	—	39.7	66.2	71.2

Compound	cmc/(g•L⁻¹)	cmc/(mmol•L⁻¹)	γ_cmc/(mN•m⁻¹)	A_min/nm²	Ref.
OC4-o-phenyl-OC4	0.14	0.14	17.6	1.01	—
	1.5	2.4	38	2.14	[24]

Compound	cmc/(g•L⁻¹)	cmc/(mmol•L⁻¹)	γ_cmc/(mN•m⁻¹)	A_min/nm²	Ref.
OC4-o-phenyl-OC4	0.14	0.14	17.6	1.01	—
	1.5	2.4	38	2.14	[24]

阳离子型Gemini氟醚表面活性剂的合成与性能表征