季铵盐氟碳表面活性剂复配体系的性能研究

doi:10.11949/0438-1157.20250097

摘要/Abstract

摘要：

为研究全氟支化短链氟碳表面活性剂复配体系性能，以全氟支化短链季铵盐氟碳表面活性剂（BQSF-IEt）和己烷磺酸钠（SHS）为研究对象，针对BQSF-IEt/SHS复配体系的临界胶束浓度（CMC）、临界表面张力（γ_CMC）、聚集行为、相互作用参数以及润湿性能进行了研究。结果表明：SHS可显著提升BQSF-IEt溶液的表面活性，当复配比（BQSF-IEt/SHS）为1∶2时溶液的表面活性最强：γ_CMC和CMC分别为16.23 mN/m和0.0065 mmol/L。同时，SHS的加入也会改变溶液中BQSF-IEt囊泡的尺寸。并且，通过Clint模型和Rubingh模型的相关计算，证明了BQSF-IEt和SHS之间存在较强的相互作用。值得注意的是，该复配体系在0.1667 mmol/L的低浓度下即实现聚四氟乙烯（PTFE）基材的完全润湿（接触角<5°），展现出作为低表面能材料高效清洗剂的潜力。

关键词: 全氟支化短链氟碳表面活性剂, 表面张力, 相互作用, 配合物, 表面活性剂, 合成

Abstract:

To investigate the performance of perfluorinated branched short chain fluorocarbon surfactant complex system, perfluorobranched short-chain quaternary ammonium fluorocarbon surfactants (BQSF-IEt) and sodium hexanesulfonate (SHS) are used as the objects, and the critical micelle concentration (CMC), critical surface tension (γ_CMC), aggregation behavior, interaction parameters, and wetting properties of the BQSF-IEt/SHS complex system are studied. The results show that SHS can significantly improve the surface activity of BQSF-IEt solution. It is worth noting that the surface activity of the solution is strongest when the compounding ratio (BQSF-IEt/SHS) is 1∶2, γ_CMC and CMC are 16.23 mN/m and 0.0065 mmol/L, respectively. At the same time, the addition of SHS will also change the size of BQSF-IEt vesicles in the solution. Moreover, through the relevant calculations of the Clint and Rubingh models, it is revealed that there is a strong interaction between BQSF-IEt and SHS. Besides, BQSF-IEt/SHS solution has strong wettability and can almost completely wet PTFE plates with low surface energy at low concentration (0.1667 mmol/L). Therefore, BQSF IEt/SHS can be used as a potential high-efficiency cleaning agent for low-energy surfaces.

Key words: perfluorobranched short chain fluorocarbon surfactant, surface tension, interaction, complexes, surfactants, synthesis

中图分类号:

TQ 072

彭梦圆, 李家明, 沙敏, 张丁. 季铵盐氟碳表面活性剂复配体系的性能研究[J]. 化工学报, 2025, 76(8): 4177-4184.

Mengyuan PENG, Jiaming LI, Min SHA, Ding ZHANG. Study on performance of quaternary ammonium fluorocarbon surfactant compound system[J]. CIESC Journal, 2025, 76(8): 4177-4184.

图/表 9

图1 BQSF-IEt的合成路线图

Fig.1 Synthesis roadmap of BQSF-IEt

图2 中间体Ⅲ和BQSF-IEt的1H NMR图

Fig.2 1H NMR spectra of intermediate Ⅲ and BQSF-IEt

图3 BQSF-IEt溶液、SHS溶液和BQSF-IEt/SHS溶液的表面张力随浓度变化曲线

Fig.3 Surface tension versus concentration of BQSF-IEt, SHS and BQSF-IEt/SHS solution

表1 BQSF-IEt/SHS复配体系的表面性能/吸附性能参数

Table 1 Surface and adsorption performance parameters of BQSF-IEt/SHS composite system

CF∶CH^①	γ_CMC/ (mN/m)	CMC^②/ (mmol/L)	Γ_max/ (10^-10 mol/cm²)	A_min/Å	$Δ G m ⊖$ / (kJ/mol)
1∶0	18.98	0.3125	1.9474	85.27	-39.99
2∶1	16.70	0.0261	3.4291	48.43	-26.15
1∶1	16.31	0.0195	3.5281	47.07	-26.87
1∶2	16.23	0.0065	4.1918	39.61	-29.59
1∶5	19.73	0.0132	4.0462	41.04	-29.58
1∶10	20.38	0.0213	4.0288	41.22	-29.37
0∶1	49.50	398	—	—	—

表1 BQSF-IEt/SHS复配体系的表面性能/吸附性能参数

Table 1 Surface and adsorption performance parameters of BQSF-IEt/SHS composite system

CF∶CH^①	γ_CMC/ (mN/m)	CMC^②/ (mmol/L)	Γ_max/ (10^-10 mol/cm²)	A_min/Å	$Δ G m ⊖$ / (kJ/mol)
1∶0	18.98	0.3125	1.9474	85.27	-39.99
2∶1	16.70	0.0261	3.4291	48.43	-26.15
1∶1	16.31	0.0195	3.5281	47.07	-26.87
1∶2	16.23	0.0065	4.1918	39.61	-29.59
1∶5	19.73	0.0132	4.0462	41.04	-29.58
1∶10	20.38	0.0213	4.0288	41.22	-29.37
0∶1	49.50	398	—	—	—

图4 SHS、BQSF-IEt和BQSF-IEt/SHS溶液的TEM图像（浓度为2倍CMC）

Fig.4 TEM images of SHS, BQSF-IE and BQSF-IEt/SHS solutions (concentration of 2 times CMC)

表2 BQSF-IEt/SHS复配体系的相互作用参数

Table 2 Interaction parameters of BQSF IEt/SHS complex system

CF∶CH^①	CMC/ (mmol/L)	CMC^ideal/ (mmol/L)	X₁	X₁^ideal	β₁₂	$l n C M C 1 C M C 2$
2∶1	0.0261	0.4685	0.6636	0.9996	-21.89	-7.1496
1∶1	0.0195	0.6245	0.6405	0.9992	-23.38
1∶2	0.0065	0.9361	0.6052	0.9954	-28.67
1∶5	0.0132	1.8677	0.5951	0.9961	-27.08
1∶10	0.0213	3.4107	0.5853	0.9922	-26.43

表2 BQSF-IEt/SHS复配体系的相互作用参数

Table 2 Interaction parameters of BQSF IEt/SHS complex system

CF∶CH^①	CMC/ (mmol/L)	CMC^ideal/ (mmol/L)	X₁	X₁^ideal	β₁₂	$l n C M C 1 C M C 2$
2∶1	0.0261	0.4685	0.6636	0.9996	-21.89	-7.1496
1∶1	0.0195	0.6245	0.6405	0.9992	-23.38
1∶2	0.0065	0.9361	0.6052	0.9954	-28.67
1∶5	0.0132	1.8677	0.5951	0.9961	-27.08
1∶10	0.0213	3.4107	0.5853	0.9922	-26.43

图5 AFM下PTFE板的形貌

Fig.5 Morphology of PTFE plate under AFM

图6 不同浓度BQSF-IEt/SHS溶液在PTFE板上的瞬时接触角

Fig.6 Instantaneous contact angles of BQSF-IEt/SHS solutions with different concentrations on PTFE plates

图7 接触角随浓度和时间的变化曲线

Fig.7 Curves of contact angle variation with concentration and time

参考文献 31

[1]	Griffiths P C, Cheung A F, Jenkins R L, et al. Interaction between a partially fluorinated alkyl sulfate and gelatin in aqueous solution[J]. Langmuir, 2004, 20(4): 1161-1167.
[2]	Yang Y W, Fang J Q, Sha M, et al. Study on foam extinguishing agents based on hydrocarbon and perfluorinated branched short-chain fluorocarbon surfactants mixed system[J]. Chemical Papers, 2021, 75(12): 6241-6255.
[3]	Szymczyk K. Properties of the ternary mixtures of fluorocarbon and hydrocarbon nonionic surfactants at the water-air interface[J]. Journal of Fluorine Chemistry, 2013, 149: 1-7.
[4]	Hussain S M S, Adewunmi A A, Mahboob A, et al. Fluorinated surfactants: a review on recent progress on synthesis and oilfield applications[J]. Advances in Colloid and Interface Science, 2022, 303: 102634.
[5]	Lee J H, Choi C H, Lee H. A universal strategy for microcapsule diversity via interfacial surfactant complexation in fluorocarbon oil-based triple emulsions[J]. Advanced Functional Materials, 2025, 35(13): 2417921.
[6]	Brahana P J, Al Harraq A, Saab L E, et al. Uptake and release of perfluoroalkyl carboxylic acids (PFCAs) from macro and microplastics[J]. Environmental Science. Processes & Impacts, 2023, 25(9): 1519-1531.
[7]	Peng M Y, Zhu H C, Sha M, et al. Effect of hydrophilic group structure on the properties of fluorinated surfactants with the same hydrophobic skeleton[J]. Applied Surface Science, 2024, 678: 161095.
[8]	林超, 潘仁明, 邢萍, 等. 新型支链型氟碳表面活性剂的合成及性能研究[J]. 有机化学, 2018, 38(12): 3260-3269.
	Lin C, Pan R M, Xing P, et al. Study on the synthesis and properties of novel branched fluorinated surfactants[J]. Chinese Journal of Organic Chemistry, 2018, 38(12): 3260-3269.
[9]	Peng M Y, Zhu H C, Sha M, et al. Surface activity, wettability and foam properties of quaternary ammonium surfactants with C—F/ Si—H double hydrophobic backbone[J]. Chemical Engineering Science, 2024, 300: 120608.
[10]	Peng M Y, Zheng M X, Sha M, et al. Surface activity, aggregation behaviour and wettability of mixtures of perfluorobranched short-chain gemini quaternary ammonium surfactant and hydrocarbon anionic surfactants in dilute solution[J]. Journal of Molecular Liquids, 2024, 413: 125942.
[11]	沙敏, 张丁, 潘仁明, 等. 含CF₃CF₂CF₂C(CF₃)₂基团支链型氟表面活性剂的合成及性能研究[J]. 化学学报, 2015, 73(5): 395-402.
	Sha M, Zhang D, Pan R M, et al. Synthesis and properties study of novel branched fluorinated surfactants with CF₃CF₂CF₂C(CF₃)₂ group[J]. Acta Chimica Sinica, 2015, 73(5): 395-402.
[12]	Peng M Y, Sha M, Zhang D, et al. Surface activity, wettability, and aggregation behavior of ecofriendly fluorocarbon surfactant based on double perfluorinated branched short chains[J]. Langmuir, 2024, 40(23): 12216-12225.
[13]	Jing D J, Bao C H, Dong Z, et al. Study on the compounding optimization of surfactants and synergistic effects on the wettability of bituminous coal[J]. Scientific Reports, 2024, 14(1): 11461.
[14]	Yang Y W, Peng M Y, Sha M, et al. Study on aqueous film-forming foam extinguishing agent based on fluorocarbon cationic-hydrocarbon anionic surfactants mixture system[J]. Journal of Surfactants and Detergents, 2022, 25(2): 205-216.
[15]	Akbari R, Antonini C. Contact angle measurements: from existing methods to an open-source tool[J]. Advances in Colloid and Interface Science, 2021, 294: 102470.
[16]	Zhou Q, Rosen M J. Molecular interactions of surfactants in mixed monolayers at the air/aqueous solution interface and in mixed micelles in aqueous media: the regular solution approach[J]. Langmuir, 2003, 19(11): 4555-4562.
[17]	Zhang Q H, Li Y L, Song Y B, et al. Adsorption behavior of branched polyoxyethylene ether carboxylate surfactants[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2018, 538: 361-370.
[18]	Wu Z F, Li P Y, Li J, et al. Interaction and properties of the synthesized anionic surfactant with CTAB: an experimental and theoretical investigation[J]. ChemistrySelect, 2020, 5(5): 1663-1670.
[19]	Zhang D, Peng M Y, Yang Y W, et al. Surface properties, aggregation behavior and wettability of the mixed system of fluorocarbon cationic surfactant and hydrocarbon anionic surfactant in dilute solutions[J]. Journal of Molecular Liquids, 2024, 405: 124957.
[20]	Clint J H. Micellization of mixed nonionic surface active agents[J]. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, 1975, 71: 1327-1334.
[21]	Holland P M, Rubingh D N. Nonideal multicomponent mixed micelle model[J]. The Journal of Physical Chemistry, 1983, 87(11): 1984-1990.
[22]	Rodakiewicz-Nowak J. Surface characteristics of some anionic, cationic, and anionic: cationic surfactants[J]. Journal of Colloid and Interface Science, 1981, 84(2): 532-535.
[23]	Sha M, Pan R M, Xing P, et al. Synthesis and surface activity study of branched fluorinated cationic (FCS), gemini (FGS) and amphoteric (FAS) surfactants with CF₃CF₂CF₂C(CF₃)₂ group[J]. Journal of Fluorine Chemistry, 2015, 169: 61-65.
[24]	Li C H, Tai X M, Guo L X, et al. Mixtures of anionic surfactants with single/triple polyoxyethylene chains and Gemini quaternary ammonium surfactant: interaction and surface activity studies[J]. Journal of Molecular Liquids, 2021, 343: 117117.
[25]	Li S J, Lai L, Mei P, et al. Equilibrium and dynamic surface properties of cationic/anionic surfactant mixtures based on bisquaternary ammonium salt[J]. Journal of Molecular Liquids, 2018, 254: 248-254.
[26]	Li L, Liu Y X, Jin X, et al. Compound anionic-nonionic surfactant system with excellent temperature and salt resistance for enhanced oil recovery[J]. Energy & Fuels, 2024, 38(2): 1047-1055.
[27]	Kanduč M, Stubenrauch C, Miller R, et al. Interface adsorption versus bulk micellization of surfactants: insights from molecular simulations[J]. J Chem Theory Comput, 2024, 20(4): 1568-1578.
[28]	Ren Z H, Luo Y, Shi D P. Mechanism on the interaction between amimo sulfonate amphoteric surfactant and sodium dodecyl benzene sulfonate in aqueous solution[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2013, 428: 18-24.
[29]	Peng M Y, Yang Y W, Sha M, et al. Surface activity, wetting and foaming properties of amine-oxidized nonionic fluorocarbon surfactant and hydrocarbon anionic surfactants mixtures at low concentrations[J]. Journal of Molecular Liquids, 2021, 343: 117701.
[30]	Shen J X, Bai Y Y, Tai X M, et al. Surface activity, spreading, and aggregation behavior of ecofriendly perfluoropolyether amide propyl betaine in aqueous solution[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(5): 6183-6191.
[31]	Dou J X, Liu J Y, Wang Y, et al. Surface activity, wetting, and aggregation of a perfluoropolyether quaternary ammonium salt surfactant with a hydroxyethyl group[J]. Molecules, 2023, 28(20): 7151.