Study on performance of quaternary ammonium fluorocarbon surfactant compound system

doi:10.11949/0438-1157.20250097

Abstract

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

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

CLC Number:

TQ 072

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.

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.

Figures/Tables 9

Fig.1 Synthesis roadmap of BQSF-IEt

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

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

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	—	—	—

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	—	—	—

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

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

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

Fig.5 Morphology of PTFE plate under AFM

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

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

References 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.

Related Articles 15

[1]	Jichao GUO, Xiaoxiao XU, Yunlong SUN. Airflow simulation and optimization based on $C O 2$ concentration in plant factory [J]. CIESC Journal, 2025, 76(S1): 237-245.
[2]	Yuntao ZHOU, Lifeng CUI, Jie ZHANG, Fuhong YU, Xingang LI, Ye TIAN. Ga₂O₃ modified CuCeO catalysts for CO₂ hydrogenation to methanol [J]. CIESC Journal, 2025, 76(8): 4042-4051.
[3]	Xinyi CHAO, Wenyao CHEN, Jing ZHANG, Gang QIAN, Xinggui ZHOU, Xuezhi DUAN. Controlled preparation and performance regulation of catalysts for one-step synthesis of methyl propionate from methanol and methyl acetate [J]. CIESC Journal, 2025, 76(8): 4030-4041.
[4]	Yufeng WANG, Xiaoxue LUO, Hongliang FAN, Baijing WU, Cunpu LI, Zidong WEI. Green organic electrosynthesis coupled with water electrolysis to produce hydrogen—overview of electrode interface regulation strategies [J]. CIESC Journal, 2025, 76(8): 3753-3771.
[5]	Yuxiang ZHOU, Qiaoli LIN. Determination of surface tension via oscillating sessile drop method [J]. CIESC Journal, 2025, 76(8): 4185-4193.
[6]	Zhengzheng GUO, Yidan ZHAO, Fuqiang WANG, Lu PEI, Yanling JIN, Fang REN, Penggang REN. Construction and electromagnetic wave absorption properties of MoS₂/RGO/NiFe₂O₄ composites with heterogeneous architecture [J]. CIESC Journal, 2025, 76(7): 3719-3732.
[7]	Liang QIAO, Shang LI, Xinliang LIU, Ming WANG, Pei ZHANG, Yingfei HOU. Synthesis and molecular simulation of terpolymer viscosity reducer for heavy oil [J]. CIESC Journal, 2025, 76(7): 3686-3695.
[8]	Bilin LIANG, Qian YU, Siqi JIA, Fang LI, Qiming LI. Structural modulation and gas separation performance of Ni-MOF-74 metal-organic framework membranes [J]. CIESC Journal, 2025, 76(6): 2714-2721.
[9]	Naisheng GUO, Xiaobo ZHU, Shuang WANG, Ping CHEN, Zhaoyang CHU, Zhichen WANG. Research progress on high and low temperature performance and influencing factors of polyurethane modified asphalt [J]. CIESC Journal, 2025, 76(6): 2505-2523.
[10]	Bing ZHANG, Jianhui LI, Xinrong MA, Yang CHEN, Jinping LI, Libo LI. Research progress of MOF preparation by steam-assisted method [J]. CIESC Journal, 2025, 76(5): 2026-2041.
[11]	Haofan ZHAO, Haojie REN, Zongkai LIU, Guanying DONG, Yatao ZHANG. Research progress of MOFs glass membranes in gas separation applications [J]. CIESC Journal, 2025, 76(5): 2042-2054.
[12]	Yaohui ZHANG, Yujie BAN, Weishen YANG. Vapor-phase synthesis and post-synthetic modification of metal-organic framework membranes [J]. CIESC Journal, 2025, 76(5): 2070-2086.
[13]	Haiqian ZHAO, Fang CHEN, Tao CHEN, Jianwei GUO, Wenjing LIN, Chufen YANG. Folate-modified pH-responsive copolymer mixed micelles for anticancer drug delivery [J]. CIESC Journal, 2025, 76(4): 1702-1710.
[14]	Yingdong ZHAO, Peijun JI, Riyao CONG, Haichao FU, Jialong ZHANG, Pengzhong CHEN, Xiaojun PENG. Preparation and high-resolution lithography study of organic tin photoresists containing acrylates [J]. CIESC Journal, 2025, 76(4): 1820-1830.
[15]	Mengfan YIN, Qian WANG, Tao ZHENG, Kui JI, Shaogui WANG, Hui GUO, Zhiqiang LIN, Rui ZHANG, Hui SUN, Haiyan LIU, Zhichang LIU, Chunming XU, Xianghai MENG, Yueping WANG. Process design of 10000 t industrial demonstration of hydrogen production from renewable energy electrolytic water - low temperature and low pressure ammonia synthesis [J]. CIESC Journal, 2025, 76(2): 825-834.