黏弹性表面活性剂（Ⅸ）—— 超长链离子型表面活性剂

doi:10.3969/j.issn.2097-2806.2026.09.002

摘要/Abstract

摘要：

超长链离子型表面活性剂通常指疏水尾链长于C₁₈且带电荷的两亲分子，其可在较低浓度下自组装为蠕虫状胶束，因而受到持续关注。本文围绕该类表面活性剂的合成、溶解性、流变行为及应用探索进行评述，涵盖阴离子、阳离子及两性离子等类型。以长链或超长链脂肪酸为起点，可经中和、酰胺化、季铵化、氧化等途径制备芥酸钠、季铵盐、磺酸甜菜碱、羧酸甜菜碱及氧化胺等产物。由于长烷基链易规整堆积并增强疏水缔合，此类化合物往往具有较高的Krafft温度和较差的水溶性。引入顺式双键、助溶盐或采用稳定性较弱的亲水头基，可削弱链间有序堆积、促进溶剂化，从而改善溶解行为。流变学研究表明，超长链离子型表面活性剂易形成缠结蠕虫状胶束网络，表现出显著的黏弹性、剪切变稀及可调的零剪切黏度；其中，芥酸钠-助溶盐体系、阳离子芥酸酰胺体系以及多种甜菜碱和氧化胺体系尤为典型。通过将易水解的酰胺键还原为C-N键，还可显著提升体系在高温强酸条件下的化学稳定性。此类流体在飞机除防冰液和低温清洁压裂液等领域展现出应用潜力，可在-20 ℃下保持蠕虫状胶束结构与功能。

关键词: 超长链表面活性剂, 离子型表面活性剂, 黏弹性表面活性剂, 蠕虫状胶束

Abstract:

Ultra-long-chain ionic surfactants, distinguished by hydrophobic tails longer than C₁₈, have emerged as a promising class of amphiphiles capable of self-assembling into wormlike micelles at relatively low concentrations. This review focuses on their synthesis, solubility, rheological behavior, and potential applications, with particular attention to anionic, cationic, and zwitterionic species. A versatile synthesis route starting from long-chain or ultra-long-chain fatty acids enables the preparation of sodium erucate, quaternary ammonium surfactants, sulfobetaines, carboxybetaines, and amine oxides. Because extended alkyl chains strengthen hydrophobic association and crystalline packing, these surfactants often suffer from high Krafft temperatures and poor water solubility. Introducing cis-unsaturated bonds, hydrotropic salts, or weakly stable hydrophilic headgroups effectively disrupts chain ordering and enhances dissolution. In particular, tetraalkylammonium hydrotropes markedly lower the Krafft temperature of sodium erucate, while betaine-type zwitterions display salt-dependent solubility governed by headgroup structure and electrostatic screening. Rheologically, ultra-long-chain ionic surfactants readily form entangled wormlike micellar networks, giving rise to pronounced viscoelasticity, shear thinning, and tunable zero-shear viscosity. The anionic sodium erucate-hydrotrope system, the cationic erucyl amide surfactant, and several zwitterionic betaines and amine oxides exemplify such behavior. Chemical stability can be improved by replacing hydrolyzable amide linkages with C-N bonds, as demonstrated by a cationic surfactant that retains viscosity in 20 wt% HCl at 150 ℃. These systems also show promise in aircraft deicing/anti-icing fluids and cryogenic clean fracturing fluids, where wormlike micelles remain functional at temperatures as low as -20 ℃.

Key words: ultra-long-chain surfactant, ionic surfactant, viscoelastic surfactant, wormlike micelles

中图分类号:

TQ423

刘璐璐, 陈强, 韩一秀, 冯玉军. 黏弹性表面活性剂（Ⅸ）—— 超长链离子型表面活性剂[J]. 日用化学工业（中英文）, 2026, 56(9): 1134-1143.

Lulu Liu, Qiang Chen, Yixiu Han, Yujun Feng. Viscoelastic surfactants (Ⅸ) Ultra-long-chain ionic surfactants[J]. China Surfactant Detergent & Cosmetics, 2026, 56(9): 1134-1143.

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参考文献 22

[1]	Tadros T F. Applied Surfactants: Principles and Applications[M]. Wiley-VCH, Weinheim, 2005.
[2]	Myers D. Surfactant Science and Technology, 3rd ed[M]. John Wiley & Sons, Hoboken, 2006.
[3]	冯玉军. 黏弹性表面活性剂(II)--蠕虫状胶束形成机理及体系构成[J]. 日用化学工业 (中英文), 2026, 56 (2) : 137-148.
[4]	Dreiss C A. Wormlike micelles: where do we stand? Recent developments, linear rheology and scattering techniques[J]. Soft Matter, 2007, 3 (8) : 956-970. doi: 10.1039/b705775j pmid: 32900044
[5]	Chu Z, Feng Y. A facile route towards the preparation of ultra-long-chain amidosulfobetaine surfactants[J]. Synthelett, 2009 (16) : 2655-2658.
[6]	Chu Z, Feng Y, Su X, et al. Wormlike micelles and solution properties of a C₂₂-tailed amidosulfobetaine surfactant[J]. Langmuir, 2010, 26(11) : 7783-7791. doi: 10.1021/la904582w pmid: 20429541
[7]	Zhang Y, Luo Y, Wang Y, et al. Single-component wormlike micellar system formed by acarboxylbetaine surfactant with C₂₂ saturated tail[J]. Colloids Surf. A, 2013, 436: 71-79. doi: 10.1016/j.colsurfa.2013.06.016
[8]	刘璐璐, 陈强, 冯玉军. 黏弹性表面活性剂(VIII)--超长链非离子表面活性剂[J]. 日用化学工业 (中英文), 2026, 56 (8) : 978-983.
[9]	Han Y X, Feng Y J, Sun H Q, et al. Wormlike micelles formed by sodium erucate in the presence of a tetraalkylammonium hydrotrope[J]. J. Phys. Chem. B, 2011, 115 (21) : 6893-6902. doi: 10.1021/jp2004634
[10]	楚宗霖, 张永民, 韩玉贵, 等. 长链阳离子表面活性剂蠕虫状胶束的剪切带转变行为研究[J]. 化学学报, 2012, 70 (15) : 1551-1554.
[11]	Wang J, Qi N, Yin H Y, et al. A robust viscoelastic surfactant tolerating 20% HCl up to 150 ℃ for oil well stimulation[J]. Pet. Sci., 2024, 21: 1865-1874. doi: 10.1016/j.petsci.2024.01.010
[12]	Zhang Y, Luo Y, Wang Y, et al. Single-component wormlike micellar system formed by acarboxylbetaine surfactant with C₂₂ saturated tail[J]. Colloids Surf. A, 2013, 436: 71-79. doi: 10.1016/j.colsurfa.2013.06.016
[13]	Liu L, Chen Q, Qian Z, et al. Cryogenic self-assembly of ultra-long-chain zwitterionic surfactants into lyotropic liquid crystals in dilute solution[J]. Colloids Surf. A, 2026, 741: 140241. doi: 10.1016/j.colsurfa.2026.140241
[14]	Chu Z, Feng J. Empirical correlations between Kraft temperature and tail length for amidosulfobetaine surfactants in the presence of inorganic salt[J]. Langmuir, 2011, 28 (4) : 1175-1181. doi: 10.1021/la204316g
[15]	冯丹. 超长链羧酸甜菜碱表面活性剂的制备及溶液性能研究[D]. 北京: 中国科学院大学, 2012.
[16]	Wang Y, Zhang Y, Liu X, et al. Effect of a hydrophilic head group on Krafft temperature, surface activities and rheological behaviors of erucyl amidobetaines[J]. J. Surfact. Deterg., 2014, 17: 295-301. doi: 10.1007/s11743-013-1496-7
[17]	楚宗霖. 基于长链磺酸甜菜碱表面活性剂的蠕虫状胶束的研究[D]. 北京: 中国科学院大学, 2011.
[18]	Zhang Y, An P, Liu X. A “worm”-containing viscoelastic fluid based on single amine oxide surfactant with an unsaturated C₂₂-tail[J]. RSC Adv., 2015, 5: 19135-19144. doi: 10.1039/C4RA16772D
[19]	Chen Q, Xu W, Liu L, et al. Cryogenic viscoelasticity of a C₂₂-tailed amine oxide across an extremely broad pH range[J]. J. Phys. Chem. B, 2026, 130 (36) : 9338-9349. doi: 10.1021/acs.jpcb.6c05256
[20]	Yin H, Feng Y, Li P, et al. Cryogenic wormlike micelles[J]. Soft Matter, 2019, 15 (12) : 2511-2516. doi: 10.1039/c9sm00068b pmid: 30839046
[21]	Yin H, Feng Y, Li P, et al. Cryogenic viscoelastic surfactant fluids: Fabrication and application in a subzero environment[J]. J. Colloid Interface Sci., 2019, 551: 89-100. doi: 10.1016/j.jcis.2019.05.011
[22]	冯玉军, 刘璐璐, 陈强, 等. 超长链氧化胺表面活性剂增稠的飞机除防冰液及其制备方法: CN 120888275 A[P]. 2025-11-04.