一种含酯基的酰胺型阳离子双子表面活性剂的合成及性能

doi:10.3969/j.issn.1001-1803.2021.07.003

摘要/Abstract

摘要：

以溴乙酸、乙二醇、月桂酸和N,N-二甲基-1,3-二氨基丙烷为原料,通过三步反应合成了一种含酯基的酰胺型阳离子双子表面活性剂C₁₂- （BAE） -C₁₂,并通过红外光谱（FT-IR）、核磁共振氢谱（¹H NMR）和质谱（MS）对产物结构进行了表征。通过表面张力、电导率和荧光3种不同方法测定了C₁₂- （BAE） -C₁₂的临界胶束浓度（cmc）,利用电导率法测定了其在25、35和45 ℃条件下的热力学函数,以及测定了其乳化和抗静电性能。结果表明,25 ℃时C₁₂- （BAE） -C₁₂在不同测定方法下的cmc分别为0.331 1、0.532 8和0.316 2 mmol/L,根据相关公式计算所得热力学参数进一步说明其胶束化过程为熵驱动,且升高温度会阻碍体系的胶束化。此外,相关应用性能测定结果还表明C₁₂- （BAE） -C₁₂与传统单链阳离子表面活性剂十二烷基三甲基溴化铵（DTAB）相比具有更好的乳化和抗静电效果。

关键词: 双子表面活性剂, 酯基季铵盐, 胶束化, 乳化性, 抗静电性

Abstract:

An amide cationic Gemini surfactant with ester groups （C₁₂- （BAE） -C₁₂） was synthesized in three steps with bromoacetic acid, ethylene glycol, lauric acid and N, N-dimethyl-1, 3-diaminopropane as raw materials. The structure of the product was characterized by FT-IR, ¹H NMR and mass spectrometry （MS）. The critical micelle concentration （cmc） of C₁₂- （BAE） -C₁₂ was determined by measurement of surface tension, conductivity and fluorescence. The thermodynamic parameters of C₁₂- （BAE） -C₁₂ were obtained from the results of conductivity at 25, 35 and 45 ℃. The emulsification and antistatic properties of C₁₂- （BAE） -C₁₂ were also measured. The results show that the cmc values of C₁₂- （BAE） -C₁₂ at 25 ℃ are 0.331 1, 0.532 8 and 0.316 2 mmol/L, respectively, as obtained by different methods. According to the results of conductivity, the thermodynamic parameters of micellization were calculated with the thermodynamic formulas. It is determined that the micellization process of C₁₂- （BAE） -C₁₂ is entropy-driven, and the increase of temperature will hinder the micellization of the surfactant. Furthermore, the results of application performance show that C₁₂- （BAE） -C₁₂ has better emulsification and antistatic effects than traditional single-chain cationic surfactant dodecyltrimethylammonium bromide （DTAB）.

Key words: Gemini surfactant, ester quaternary ammonium salt, micellization, emulsifying property, antistatic property

中图分类号:

TQ423

陆小豪,许虎君,林良良,常宽,高海燕. 一种含酯基的酰胺型阳离子双子表面活性剂的合成及性能[J]. 日用化学工业, 2021, 51(7): 598-605.

Lu Xiaohao,Xu Hujun,Lin Liangliang,Chang Kuan,Gao Haiyan. Synthesis and properties of an amide cationic Gemini surfactant with ester groups[J]. China Surfactant Detergent & Cosmetics, 2021, 51(7): 598-605.

图/表 9

图 1

图 2

图 3

图 4

表1

表2

图 5

图 6

图 7

参考文献 20

[1]	Akram M, Anwar S, Ansari F, et al. Bio-physicochemical analysis of ethylene oxide-linked diester-functionalized green cationic Gemini surfactants[J]. RSC Advances, 2016,6(26) : 21697-21705. doi: 10.1039/C5RA28129F
[2]	Tehrani-Bagha A R, Holmberg K. Cationic ester-containing Gemini surfactants physical-chemical properties[J]. Langmuir, 2010,26(12) : 9276-9282. doi: 10.1021/la1001336 pmid: 20387872
[3]	Zana R. Gemini (dimeric) surfactants[J]. Current Opinion in Colloid and Interface Science, 1996,1(5) : 566-571. doi: 10.1016/S1359-0294(96)80093-8
[4]	Menger F M, Keiper J S. Gemini surfactants[J]. Angewandte Chemie International Edition, 2000,39(11) : 1906-1920. doi: 10.1002/(ISSN)1521-3773
[5]	Xu Hujun, Kang Peng, Wang Zhongcai, et al. Synjournal and properties of cationic ester-containing Gemini surfactants[J]. Tenside Surfactants Detergents, 2013,50(5) : 385-390. doi: 10.3139/113.110271
[6]	Sun Ya, Pan Hua, Han Fu, et al. Synjournal and properties of quaternary ammonium Gemini surfactants with hydroxyl in headgroups[J]. China Surfactant Detergent & Cosmetics, 2019,49(3) : 135-140.
[7]	Chauhan V, Singh S, Mishra R, et al. Synjournal and bio-physicochemical properties of amide-functionalized N-methylpiperazinium surfactants[J]. Journal of Colloid and Interface Science, 2014,436:122-131. doi: 10.1016/j.jcis.2014.08.029 pmid: 25268815
[8]	Zhu Zheng, Lu Xiaohao, Xu Hujun, et al. Synjournal and properties of cationic Gemini surfactants with amide groups[J]. Tenside Surfactants Detergents, 2020,57(4) : 332-339.
[9]	Liu Hongqin, Zhou Xiqin, Zhang Xiaoyu, et al. Green synjournal, surface activity, micellar aggregation, and corrosion inhibition properties of new Gemini quaternary ammonium surfactants[J]. Journal of Chemical and Engineering Data, 2018,63(5) : 1304-1315. doi: 10.1021/acs.jced.7b00911
[10]	Bhadani A, Tani M, Endo T, et al. New ester based Gemini surfactants: the effect of different cationic headgroups on micellization properties and viscosity of aqueous micellar solution[J]. Physical Chemistry Chemical Physics, 2015,17(29) : 19474-19483. doi: 10.1039/C5CP02115D
[11]	Bhadani A, Endo T, Sakai K, et al. Synjournal and dilute aqueous solution properties of ester functionalized cationic Gemini surfactants having different ethylene oxide units as spacer[J]. Colloid and Polymer Science, 2014,292(7) : 1685-1692. doi: 10.1007/s00396-014-3233-9
[12]	Fang Yun, Xia Yongmei, Zhou Jiandong, et al. Synjournal and properties of fatty amide propyl dimethyl amine oxide[J]. China Surfactant Detergent & Cosmetics, 1996.
[13]	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(11) : 4555-4562. doi: 10.1021/la020789m
[14]	Zana R. Critical micellization concentration of surfactants in aqueous solution and free energy of micellization[J]. Langmuir, 1996,12(5) : 1208-1211. doi: 10.1021/la950691q
[15]	Das S, Naskar B, Ghosh S. Influence of temperature and organic solvents (isopropanol and 1,4-dioxane) on the micellization of cationic Gemini surfactant (14-4-14)[J]. Soft Matter, 2014,10(16) : 2863-2875. doi: 10.1039/c3sm52938j
[16]	Du Xiaohao, Xu Wei, Du Xuejie. Effect of antistatic performance for fabric conditioner[J]. China Surfactant Detergent & Cosmetics, 2002 (4) : 84-86.
[17]	Wettig S D, Li X, Verrall R E. Thermodynamic and aggregation properties of Gemini surfactants with ethoxylated spacers in aqueous solution[J]. Langmuir, 2003,19(9) : 3666-3670. doi: 10.1021/la0340100
[18]	Zhong Xing, Guo Jianwei, Feng Lijuan, et al. Cationic Gemini surfactants based on adamantane: synjournal, surface activity and aggregation properties[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2014,441:572-580. doi: 10.1016/j.colsurfa.2013.10.016
[19]	Ray G B, Chakraborty I, Moulik S P. Pyrene absorption can be a convenient method for probing critical micellar concentration (cmc) and indexing micellar polarity[J]. Journal of Colloid and Interface Science, 2006,294(1) : 248-254. doi: 10.1016/j.jcis.2005.07.006
[20]	Xiao Jinxin, Zhao Zhenguo. The applied principle of surfactants [M]. Beijing: Chemical Industry Press, 2003: 199-239.

T/K	cmc/ （mmol·L^-1）	β	ΔG⁰_m/ （kJ·mol^-1）	ΔH⁰_m/ （kJ·mol^-1）	-TΔS⁰_m/ （kJ·mol^-1）
298.15	0.533	0.481	-36.66	-7.98	-28.68
308.15	0.562	0.369	-33.32	-7.55	-25.77
318.15	0.595	0.407	-35.64	-8.40	-27.24