一种酰胺型Gemini表面活性剂的合成及性能

doi:10.3969/j.issn.1001-1803.2020.03.001

摘要/Abstract

摘要：

以十二胺、丙烯酸甲酯、2,6-吡啶二甲酸为主要原料,经过加成、酰胺化、皂化等反应合成了一种酰胺型Gemini表面活性剂N,N’-双十二烷基-2,6-吡啶二酰胺丙酸钠（DLP-12）。经单因素变量考察得出该反应的最佳反应条件为：n（N-十二烷基-β-氨基丙酸甲酯）∶n（2,6-吡啶二甲酰氯）=2.4∶1,40 ℃下回流反应8 h。在此条件下DLP-12的产率为68.14%。性能测定的结果表明,在25,35和45 ℃时,此种新型Gemini表面活性剂的临界胶束浓度分别为9.1×10 ^-5,9.5×10 ^-5和9.7×10 ^-5mol/L,与之对应的表面张力分别为33.7,32.4和31.1 mN/m,最大表面过剩（Γ_max）随着温度的升高而减小,临界堆积参数（CPP）的值表明表面活性剂自组装形态实现由层状结构向棒状结构过渡。25 ℃时,以液体石蜡和正辛烷作为油相所测得的乳化性能分别为277和252 s,罗氏泡沫高度为141 mm。

关键词: N, N’-双十二烷基-2;, 6-吡啶二酰胺丙酸钠, 十二胺, 加成, 酰胺化, 2, 6-吡啶二甲酸, Gemini表面活性剂

Abstract:

An amide Gemini surfactant N,N’-bis-dodecyl-2,6-pyridinium dimethylamide propionate sodium（DLP-12） was synthesized from dodecylamine, methyl acrylate, and 2, 6-pyridine-dicarboxylic acid by addition, amidation, and saponification reactions. By single factor experiments, the optimum reaction conditions for this reaction were: n（N-dodecyl-β-alanine-methyl ester）∶n（2, 6-pyridine-dicarboxylic acid）=2.4∶1, reflux reaction at 40 ℃ for 8 hours. Under these conditions, the yield of the final product was 68.14%. The results showed that the critical micelle concentrations of DLP-12 were 9.1×10 ^-5, 9.5×10 ^-5and 9.7×10 ^-5mol/L at 25, 35 and 45 ℃, respectively, and the corresponding surface tension were 33.7, 32.4 and 31.1 mN/m, respectively. The maximum surface excess concentration （Γ_max） decreased with the increase of temperature. The value of the critical packing parameter （CPP） indicated the self-assembly morphology of surfactants in aqueous solution transformed from lamellar structure to rod-like structure. At 25 ℃, the emulsification properties measured with liquid paraffin and n-octane as the oil phase were 277 and 252 s, respectively, and the Roche foam height was 141 mm.

Key words: N, N’-bis-dodecyl-2;, 6-pyridinium dimethylamide propionate sodium, dodecylamine, addition, amidation, 2, 6-pyridine-dicarboxylic acid, Gemini surfactant

中图分类号:

TQ423

蔡永晨,郑华生,许虎君. 一种酰胺型Gemini表面活性剂的合成及性能[J]. 日用化学工业, 2020, 50(3): 143-148.

Yong-chen CAI,Hua-sheng ZHENG,Hu-jun XU. Synthesis and properties of an amide Gemini surfactant[J]. China Surfactant Detergent & Cosmetics, 2020, 50(3): 143-148.

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参考文献 21

[1]	Menger F M, Littau C A . Gemini surfactants: a new class of self-assembling molecules[J]. Journal of the American Chemical Society, 1993,115(22) : 10083-10090.
[2]	Menger F M, Littau C A . Gemini-surfactants: synjournal and properties[J]. Journal of the American Chemical Society, 1991,113(4) : 1451-1452.
[3]	Manne S, Schäffer T E, Huo Q , et al. Gemini Surfactants at solid-liquid interfaces: control of interfacial aggregate geometry[J]. Langmuir, 1997,13(24) : 6382-6387.
[4]	Rosen M J . Surfactants and interfacial phenomena[J]. Journal of Colloid & Interface Science, 2004,68(1) : 347.
[5]	Zana R, Xia J . Gemini surfactants: synjournal, interfacial and solution-phase behavior, and applications[J]. Journal of Colloid & Interface Science, 2003,272(2) : 502.
[6]	Zana R . Dimeric (Gemini) surfactants: Effect of the spacer group on the association behavior in aqueous solution[J]. Journal of Colloid & Interface Science, 2002,248(2) : 203-220.
[7]	Lucía C D, Rodrigues M , et al. Gemini imidazolium amphiphiles for the synjournal, stabilization, and drug delivery from gold nanoparticles[J]. Langmuir, 2012,28(5) : 2368-2381.
[8]	Wattebled L, André Laschewsky . New anionic gemini surfactant based on EDTA accessible by convenient synjournal[J]. Colloid & Polymer Science, 2007,285(12) : 1387-1393.
[9]	Zana R, Xia J . Gemini surfactants: synjournal, interfacial and solution-phase behavior, and applications[J]. Journal of Colloid & Interface Science, 2003,272(2) : 502.
[10]	Marcelo C Murguía, Cristaldi M D, Ayelén Porto , et al. Synjournal, surface-active properties, and antimicrobial activities of new neutral and cationic trimeric surfactants[J]. Journal of Surfactants and Detergents, 2008,11(1) : 41-48.
[11]	Yao Zhigang, Li Ganzuo, Dong Fenglan , et al. Progress in synjournal of Gemini surfactants[J]. Progress in Chemistry, 2004,16(6) : 349-364.
[12]	Misiak P, Bożenna Różycka-Roszak, Mozrzymas A , et al. Effect of a carboxylic group on the conformational properties of some Gemini surfactants[J]. Journal of Solution Chemistry, 2007,36(7) : 845-851.
[13]	Huang Zhi, Li Chenghai, Liang Yuning , et al. Improvement on the synthetic method of N, N’-dilauroyl ethylenediamine- diacetic acid[J]. Fine Chemicals, 2002,19(1) : 1-3.
[14]	Wang Peiyi, Yin Hao, Zhang Yingjun , et al. Synjournal and properties of amide gemini surfactant[J]. Fine Chemicals, 2009,26(9) : 863-866.
[15]	Wang Peiyi, Yin Hao, Zhang Yingjun . Synjournal and properties of sodium dilauroy terephthalamide propionate acid[J]. Fine Chemicals, 2010,27(7) : 650-653.
[16]	Wang Lijie, Zhang Zun . Production technology and analysis of market of terephthaloyl chloride[J]. China Chlor-Alkali, 2017 ( 9) : 22-24.
[17]	Yu Xuejun, Xu Dan . Synjournal and properties of sodium N-dodecyl-β-aminopropionate[J]. Fine Chemicals, 1996 ( 6) : 16-17.
[18]	Islam M S, Shortall S M, Mekhail G M , et al. Effect of counterions on the micellization and monolayer behaviour of cationic gemini surfactants[J]. Phys Chem Chem Phys, 2017,19(17) , 10825-10834.
[19]	Wang H, Wettig S D . Synjournal and aggregation properties of dissymmetric phytanyl-Gemini surfactants for use as improved DNA transfection vectors[J]. Phys Chem Chem Phys, 2010,13(2) : 637-642.
[20]	Myers D . Surfactant science and technology[J]. Talanta, 2005,51(3) : 609.
[21]	Sun Y, Ding L, Zhou J , et al. Synjournal and properties of α-sulfo carboxyl disodium salt[J]. Journal of Dispersion Science and Technology, 2018,39(9) : 1360-1366.

温度/℃	cmc/ （mol·L^-1）	γ_cmc/ （mN·m^-1）	Γ_max×10¹⁰/ （mol·cm^-2）	A_min/nm²	pc₂₀	CPP	自组装形状
25	9.1×10^-5	33.7	2.561	0.648	4.378	0.648	层状
35	9.5×10^-5	32.4	1.801	0.922	4.447	0.455	棒状
45	9.7×10^-5	31.1	1.745	0.952	4.568	0.441	棒状

表面活性剂	cmc/（mol·L^-1）	γ_cmc/（mN·m^-1）
DLP-12	9.1×10^-5	33.7
CTAB	9.8×10^-4	37.3
SDS	8.0×10^-3	32.0
APPZ-12	8.3×10^-4	32.7

表面活性剂	泡沫高度/mm		乳化性/s
表面活性剂	起始高度	5 min后	液体石蜡	正辛烷
DLP-12	141	138	277	252
CTAB	122	116	159	196
SDS	138	133	226	36
APPZ-12	212	208	223	214