咪唑离子液体与辛烷磺酸钠复配体系的聚集行为

doi:10.3969/j.issn.2097-2806.2024.08.002

摘要/Abstract

摘要：

采用表面张力法测定了辛烷磺酸钠（SOS）/溴化1-癸基-3-甲基咪唑鎓（[C₁₀mim]Br）以及SOS/溴化1-十四烷基-3-甲基咪唑鎓（[C₁₄mim]Br）复配体系的表面活性，得到了临界胶束浓度（cmc）、平衡表面张力（γ_cmc）、表面压（Π_cmc）、饱和吸附量（Γ_max）和气液界面吸附分子的最小截面积（A_min）等参数。应用Rubingh正规溶液理论，计算了混合胶束的组成（X₁^m）、活度系数（f₁^m和f₂^m）及分子相互作用参数（β^m），所研究的体系均表现出了强协同增效作用，与[C₁₀mim]Br相比，SOS与[C₁₄mim]Br间的相互作用更强。热力学参数的计算结果也表明了混合胶束是自发形成的，且为热力学稳定体系。利用分光光度法测定了体系的浊度，结合目视观察与吸光度数值绘制了各体系的相图，SOS与[C₁₀mim]Br和[C₁₄mim]Br的复配体系均存在3个浓度区，即低均相溶液区、两相区和高均相溶液区。

关键词: 表面活性离子液体, 混合胶束, 聚集行为, 协同作用

Abstract:

Two mixed systems consisting of an anionic surfactant and a cationic surface-active ionic liquid were studied. The mixture of sodium octanesulfonate （SOS） and 1-decyl-3-methylimidazolium bromide （[C₁₀mim]Br）, and the mixture of SOS and 1-tetradecyl-3-methylimidazolium bromide （[C₁₄mim]Br）, were both investigated using surface tension measurement. The parameters, such as critical micelle concentration （cmc）, surface tension at cmc （γ_cmc）, surface pressure at cmc （Π_cmc）, maximum surface excess （Γ_max） and minimum area per molecule （A_min）, were obtained. The mixed micellar parameters including micellar mole fraction （X₁^m）, micellar interaction parameters （β^m） and activity coefficients （f₁^m and f₂^m） were calculated by applying Rubingh’s regular solution theory. The calculated parameters confirmed that there were strong synergy in all these mixed systems, and the interaction of SOS with [C₁₄mim]Br was stronger than that with [C₁₀mim]Br. Thermodynamic parameters for mixed monolayers and mixed micelles were calculated and discussed, which indicated that the mixed micelles were spontaneously formed and were thermodynamically stable systems. Turbidity measurement was conducted using spectrophotometry. The phase diagrams were plotted for each system based on visual observations and absorbance values. The mixed systems of SOS/[C₁₀mim]Br and SOS/[C₁₄mim]Br all exhibited three concentration regions: a low-concentration homogeneous solution region, a two-phase region, and a high-concentration homogeneous solution region.

Key words: surface-active ionic liquid, mixed micelle, aggregation behavior, synergism

中图分类号:

TQ423

赵学艳,黄静宜,肖瑞杰,曹桂荣. 咪唑离子液体与辛烷磺酸钠复配体系的聚集行为[J]. 日用化学工业（中英文）, 2024, 54(8): 887-894.

Xueyan Zhao,Jingyi Huang,Ruijie Xiao,Guirong Cao. Aggregation behavior of mixed systems of imidazolium-based ionic liquid and sodium octanesulfonate[J]. China Surfactant Detergent & Cosmetics, 2024, 54(8): 887-894.

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参考文献 29

[1]	Zhao Xueyan, Xiao Ruijie, Cao Guirong. Micelle systems based on surface active ionic liquids[J]. Chemistry (Huaxue Tongbao), 2022, 85 (10) : 1209-1218.
[2]	Yang Xushao, Wang Jun, Fang Yun. Synthesis and surface activities of asymmetrical Gemini ionic liquid-based surfactants[J]. China Surfactant Detergent & Cosmetics, 2019, 49 (5) : 279-285.
[3]	Cui Hui, Tu Yan, Shang Yazhuo, et al. Syntheses and aggregation behaviors of ionic liquid surfactants 1-butyl-3-methylimidazolium alkyl sulfate[J]. Chemistry (Huaxue Tongbao), 2017, 80 (7) : 672-678.
[4]	Cornellas A, Perez L, Comelles F, et al. Self-aggregation and antimicrobial activity of imidazolium and pyridinium based ionic liquids in aqueous solution[J]. Journal of Colloid and Interface Science, 2011, 355: 164-171. doi: 10.1016/j.jcis.2010.11.063 pmid: 21186035
[5]	Dong Bin, Zhao Xueyan, Zheng Liqiang, et al. Aggregation behavior of long-chain imidazolium ionic liquids in aqueous solution: micellization and characterization of micelle microenvironment[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2008, 317: 666-672.
[6]	Wang Bingying, Zhu Zaisheng, Yin Jiayu, et al. Microemulsion system formed with new piperazinium-based surface-active ionic liquid[J]. Journal of Molecular Liquids, 2023, 371: 121103-121111.
[7]	Zhao Xueyan, Xiao Ruijie, Cao Guirong. Effect of cosolvents on the self-assembly of L64 in imidazolium ionic liquid[J]. Chemical Research and Application, 2023, 35 (7) : 1617-1623.
[8]	Zhao Xueyan. The effect of cyclohexane on the phase behavior of 64/1-butyl-3-methylimidazolium tetrafluoroborate system[J]. Journal of Dispersion Science and Technology, 2015, 36: 1080-1085.
[9]	Yang Jiaen, Huang Haijun, Zheng Jiangen, et al. Effect of head group of surfactant on the self-assembly structures and aggregation transitions in a mixture of cationic surfactant and anionic surfactant-like ionic liquid[J]. Journal of Molecular Liquids, 2020, 308: 112995-113003.
[10]	Ghosh S, Ghatak C, Banerjee C, et al. Aggregation behavior and antimicrobial activity of ester-functionalized imidazolium-and pyridinium-based ionic liquids in aqueous solution[J]. Langmuir, 2013, 29: 10066-10076.
[11]	Pal A, Punia R. Self-aggregation behaviour of cationic surfactant tetradecyltrimethylammonium bromide and bi-amphiphilic surface active ionic liquid 3-methyl-1-pentylimidazolium dodecylsulfate in aqueous solution[J]. Journal of Molecular Liquids, 2020, 304: 112803-112809.
[12]	Padsala S, Patel V I, Ray D, et al. Mixed micelles of sodium perfluorooctanoate and imidazolium based ionic liquids in aqueous solution: A SANS and Tensiometric study[J]. Journal of Molecular Liquids, 2021, 322: 114558-114567.
[13]	Dutta R, Ghosh S, Banerjee P. Micelle-vesicle-micelle transition in aqueous solution of anionic surfactant and cationic imidazolium surfactants: alteration of the location of different fluorophores[J]. Journal of Colloid and Interface Science, 2017, 490: 762-773. doi: S0021-9797(16)31002-5 pmid: 27997846
[14]	Javadian S, Nasiri F, Heydari A, et al. Modifying effect of imidazolium-based ionic liquids on surface activity and self-assembled nanostructures of sodium dodecyl sulfate[J]. Journal of Physical Chemistry B, 2014, 118: 4140-4150.
[15]	Gehlot P S, Rao K S, Bharmoria P, et al. Spontaneous formation of multiarchitecture vesicles of [C₈mim]Br+[Na]DBS in aqueous medium: synergic interplay of electrostatic, hydrophobic, and π-π stacking interactions[J]. Journal of Physical Chemistry B, 2015, 119: 15300-15309.
[16]	Garcia M T, Ribosa I, González J J. Surface activity, self-aggregation and antimicrobial activity of catanionic mixtures of surface active imidazolium-or pyridinium-based ionic liquids and sodium bis(2-ethylhexyl) sulfosuccionate[J]. Journal of Molecular Liquids, 2020, 303: 112637-112648.
[17]	Maiti K, Bhattacharya S, Moulik S, et al. Physicochemical studies on ion-pair amphiphiles: solution and interfacial behaviour of systems derived from sodium dodecylsulfate and n-alkyltrimethylammonium bromide homologues[J]. Journal of Chemical Sciences, 2010, 122: 867-879.
[18]	Herrington K L, Kaler E W. Phase behavior of aqueous mixtures of dodecyltrimethylammonium bromide (DTAB) and sodium dodecyl sulfate (SDS)[J]. Journal of Physical Chemistry, 1993, 97: 13792-13802.
[19]	Pal A, Yadav S. Effect of cationic polyelectrolyte poly(diallyldimethylammonium chloride) on micellization behavior of anionic surface active ionic liquid 1-butyl-3-methylimidazolium dodecylsulfate [C₄mim][C₁₂SO₄] in aqueous solutions[J]. Colloid and Polymer Science, 2018, 296: 1635-1650.
[20]	Klevens H. B. Critical micelle concentrations as determined by refraction[J]. Journal of Physical Chemistry, 1948, 52: 130-148.
[21]	Holland P M, Rubingh D N. Nonideal multicomponent mixed micelle model[J]. Journal of Physical Chemistry, 1983, 87: 1984-1990.
[22]	Rosen M J, Hua Xiyuan. Surface concentrations and molecular interactions in binary mixtures of surfactants[J]. Journal of Colloid and Interface Science, 1982, 86: 164-172.
[23]	Xiao Jinxin, Zhao Guoxi. Phase behavior of aqueous mixtures of cationic-anionic surfactants[J]. Acta Physico-Chimica Sinica, 1995, 11 (9) : 818-823.
[24]	Mahbub S, Rahman M, Rana S, et al. Aggregation behavior of sodium dodecyl sulfate and cetyltrimethylammonium bromide mixtures in aqueous/chitosan solution at various temperatures: an experimental and theoretical approach[J]. Journal of Surfactants and Detergents, 2019, 22: 137-152.
[25]	Pal A, Punia R. Interaction study of mixed micellar system of isoquinoline based surface active ionic liquids and cationic surfactant in aqueous medium[J]. Colloid and Polymer Science, 2019, 297: 1011-1024.
[26]	Zhou Qiong, 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: 4555-4562.
[27]	Rosen M J, Zhou Qiong. Surfactant-surfactant interactions in mixed monolayer and mixed micelle formation[J]. Langmuir, 2001, 17: 3532-3537.
[28]	Sohrabi B, Gharibi H, Tajik B, et al. Molecular interactions of cationic and anionic surfactants in mixed monolayers and aggregates[J]. Journal of Physical Chemistry B, 2008, 112: 14869-14876.
[29]	Shah M U H, Sivapragasam M, Moniruzzaman M, et al. Aggregation behavior and antimicrobial activity of a micellar system of binary ionic liquids[J]. Journal of Molecular Liquids, 2018, 266: 568-576.

System	α_SOS	cmc/（mmol/L）	γ_cmc/（mN/m）	pc₂₀	Π_cmc/（mN/m）	Γ_max/（μmol/m²）	A_min/nm²
SOS/[C₁₀mim]Br	0	38.10	31.86	-0.73	40.14	1.80	0.92
	0.2	8.87	20.73	0.51	51.27	1.76	0.94
	0.4	6.60	19.81	0.46	52.19	2.01	0.82
	0.6	7.21	20.50	0.35	51.50	2.00	0.82
	0.8	9.70	21.26	0.44	50.74	1.76	0.94
	1.0	157.44	36.58	-1.59	35.42	2.05	0.81
SOS/[C₁₄mim]Br	0	1.92	37.22	0.44	34.78	1.75	0.95
	0.2	0.53	26.23	1.30	45.77	2.13	0.78
	0.4	0.51	25.88	1.36	46.12	2.20	0.75
	0.6	0.53	24.77	1.40	47.23	1.96	0.85
	0.8	0.63	25.33	1.24	46.67	2.06	0.81
	1.0	157.44	36.58	-1.59	35.42	2.05	0.81

System	α_SOS	cmc/（mmol/L）		X₁^m	β^m	f₁^m	f₂^m	X₁⁰	β^σ
System	α_SOS	C^m_Expm	C^m_Theor	X₁^m	β^m	f₁^m	f₂^m	X₁⁰	β^σ
SOS/[C₁₀mim]Br	0.2	8.87	8.79	0.37	-8.90	0.029	0.30	0.39	-13.69
	0.4	6.60	6.48	0.42	-9.75	0.038	0.18	0.42	-13.82
	0.6	7.21	7.11	0.45	-9.58	0.058	0.14	0.45	-13.83
	0.8	9.7	9.68	0.50	-9.14	0.10	0.10	0.48	-14.33
SOS/[C₁₄mim]Br	0.2	0.53	0.51	0.30	-12.82	0.001 9	0.32	0.35	-17.07
	0.4	0.51	0.54	0.34	-12.29	0.004 7	0.24	0.37	-16.74
	0.6	0.53	0.48	0.37	-13.44	0.004 8	0.16	0.39	-17.11
	0.8	0.63	0.59	0.40	-13.83	0.006 9	0.11	0.42	-17.49

System	α_SOS	$\Delta G_{\mathrm{mic}}^{\ominus}$ / （kJ/mol）	$\Delta G_{\mathrm{ad}}^{\ominus}$ / （kJ/mol）	G_min/ （kJ/mol）	?G_ex/ （kJ/mol）
SOS/[C₁₀mim]Br	0	-18.5	-40.8	17.65	—
	0.2	-21.66	-50.79	11.73	-5.13
	0.4	-22.40	-48.36	9.78	-5.87
	0.6	-22.18	-47.93	10.12	-5.86
	0.8	-21.44	-50.27	12.03	-5.86
	1.0	-14.53	-31.81	17.84	—
SOS/[C₁₄mim]Br	0	-25.46	-45.33	21.29	—
	0.2	-28.65	-50.14	12.32	-6.64
	0.4	-28.74	-49.70	11.69	-6.85
	0.6	-28.65	-52.75	12.68	-7.76
	0.8	-28.22	-50.88	12.36	-8.22
	1.0	-14.53	-31.81	17.84	—