非对称Gemini离子液体表面活性剂的制备及表面活性

doi:10.3969/j.issn.1001-1803.2019.05.001

日用化学工业 ›› 2019, Vol. 49 ›› Issue (5): 279-285.doi: 10.3969/j.issn.1001-1803.2019.05.001

• 基础研究 • 下一篇

非对称Gemini离子液体表面活性剂的制备及表面活性

杨许召^1,²,王军²,方云¹()

^1. 江南大学化学与材料工程学院合成与生物胶体教育部重点实验室,江苏无锡 214122
^2. 郑州轻工业学院材料与化学工程学院郑州市精细化学品重点实验室,河南郑州 450002

收稿日期:2019-01-25 修回日期:2019-04-30 出版日期:2019-05-22 发布日期:2019-05-24
通讯作者: 方云
作者简介:杨许召（1978-）,男,博士研究生,电话：（0371）86609676,E-mail：yangxz@zzili.edu.cn。
基金资助:
河南省科技攻关项目资助(162102210056);"十二五"国家科技支撑计划资助项目(2013BAC01B04);郑州市科技项目资助(141PQYJS555)

Synthesis and surface activities of asymmetrical Gemini ionic liquid-based surfactants

YANG Xu-zhao^1,²,WANG Jun²,FANG Yun¹()

^1. Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, Jiangsu 214122, China
^2. Zhengzhou Key Laboratory of Fine Chemicals, School of Material and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou, Henan 450002, China

Received:2019-01-25 Revised:2019-04-30 Online:2019-05-22 Published:2019-05-24
Contact: Yun FANG

摘要/Abstract

摘要：

以咪唑、溴代烷、1,3-二溴丙烷和长链烷基N,N-二甲基叔胺分别经取代反应和季铵化反应制备出非对称Gemini离子液体表面活性剂[C_nIMC₃N₁₁_n][Br]₂（n=10,12,14,16）,并通过 ¹H NMR、 ¹³C NMR和元素分析确定其化学结构。测定了其Krafft点,发现随着疏水链链长的增加,Krafft点逐渐升高。采用吊片法测定了产物的表面活性,结果表明,所制备的Gemini离子液体表面活性剂具有优良的表面活性,其γ_cmc在35 mN/m左右,cmc在10 ^-4~10 ^-3 mol/L范围内,比普通阳离子表面活性剂的cmc低1~2个数量级。通过电导率法测定了[C_nIMC₃N₁₁_n][Br]₂的cmc和反离子结合度（β）,由电导率法测得的cmc值稍高于吊片法测得的数据,表明形成了无表面活性的预胶束聚集体;同时随着温度的增加,cmc值增加、β值降低,这是因为温度的升高降低了其形成胶束的能力和已形成胶束的稳定性。

关键词: Gemini表面活性剂, 离子液体, 制备, 表面活性

Abstract:

Asymmetrical Gemini ionic liquid-based surfactants,[C_nIMC₃N₁₁_n][Br]₂（n=10, 12, 14, 16）, were prepared with imidazole, bromoalkane, 1,3-dibromopropane and long-chain alkyl N,N-dimethyl tertiary amine as raw materials through substitution reaction and quaternization reaction, respectively. The chemical structures of these Gemini ionic liquid-based surfactants were characterized and identified by ¹H NMR, ¹³C NMR and elemental analysis. The Kraff points were determined and it was found that the Krafft points gradually increased as the hydrophobic chain length increased. Surface activities of[C_nIMC₃N₁₁_n][Br]₂ were measured by Wilhelmy plate method. The results show that[C_nIMC₃N₁₁_n][Br]₂ display good surface active performance. The values of γ_cmc of [C_nIMC₃N₁₁_n][Br]₂ are approximately 35 mN/m and those of cmc are between 10 ^-4 mol/L and 10 ^-3 mol/L, which are 1 to 2 orders of magnitude lower than the traditional cationic surfactants. The values of cmc and counterion binding degree（β）were determined by electrical conductivity method. The cmc values measured by conductivity method were slightly higher than that measured by Wilhelmy plate method, indicating the existence of nonsurface-active premicellar aggregates. Meanwhile, cmc values increase and β values decrease as the temperature increases because of the reduction of the ability to form micelles and the stability of the formed micelles.

Key words: Gemini surfactants, ionic liquid, preparation, surface activity

中图分类号:

TQ423.12

杨许召,王军,方云. 非对称Gemini离子液体表面活性剂的制备及表面活性[J]. 日用化学工业, 2019, 49(5): 279-285.

YANG Xu-zhao,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.

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参考文献 17

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表面活性剂	Krafft点/ ℃
[C₁₀IMC₃N₁₁₁₀][Br]₂	<0
[C₁₂IMC₃N₁₁₁₂][Br]₂	5
[C₁₄IMC₃N₁₁₁₄][Br]₂	12
[C₁₆IMC₃N₁₁₁₆][Br]₂	23

表面活性剂	cmc/（mmol·L^-1）	γ_cmc/（mN·m^-1）	Γ_max/（μmol·m^-2）	A_min/nm²	pc₂₀
[C₁₀IMC₃N₁₁₁₀][Br]₂	4.693	32.77	1.29	1.287	3.35
[C₁₂IMC₃N₁₁₁₂][Br]₂	0.710	34.73	1.16	1.432	4.24
[C₁₄IMC₃N₁₁₁₄][Br]₂	0.115	35.12	1.09	1.523	5.14
[C₁₆IMC₃N₁₁₁₆][Br]₂	0.015	35.79	1.05	1.582	5.61

表面活性剂	35 ℃			45 ℃
表面活性剂	cmc/（mmol·L^-1）	α	β	cmc/（mmol·L^-1）	α	β
[C₁₀IMC₃N₁₁₁₀][Br]₂	6.211	0.315	0.685	6.366	0.401	0.599
[C₁₂IMC₃N₁₁₁₂][Br]₂	0.815	0.320	0.680	0.827	0.393	0.607
[C₁₄IMC₃N₁₁₁₄][Br]₂	0.114	0.328	0.672	0.123	0.384	0.616
[C₁₆IMC₃N₁₁₁₆][Br]₂	0.013	0.384	0.616	0.017	0.477	0.523

非对称Gemini离子液体表面活性剂的制备及表面活性

Synthesis and surface activities of asymmetrical Gemini ionic liquid-based surfactants

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