基于三乙烯二胺新型表面活性剂的合成及性能研究

doi:10.3969/j.issn.1001-1803.2021.01.004

摘要/Abstract

摘要：

三乙烯二胺分别与正溴代十二、十四、十六烷反应获得单季铵盐,再与氯乙酸乙酯反应,经碱性水解、纯化后获得一类新型杂表面活性剂2-（4-烷基-1,4-二氮杂二环[2.2.2]辛烷）乙酸盐溴化物（结构式为BrC_nH₂_n₊₁N（CH₂CH₂） ₃NCH₂COO,n=12,14,16,命名为3a,3b,3c）,总收率分别为78.8%,80.6%和83.0%（以三乙烯二胺计）。采用NMR,ESI-MS和FT-IR表征了结构,并研究了其表面性能和热力学参数。结果表明：298.15 K下,电导率法测定了3a,3b和3c的cmc值分别为0.627,0.576和0.502 mmol/L （经验方程为：cmc=1.005 3-0.031 25 n）;悬滴法测定了γ_cmc分别为38.23,37.83和36.65 mN/m （经验方程为γ_cmc=43.10-0.395 n）;其Krafft点分别为6,10和13 ℃,温度适应范围广;起泡性和泡沫稳定性良好,其中3c的起始泡高为100 mm,30 min后降至61 mm;其乳化时间分别为260,348和485 s。由热力学参数计算表明,胶束形成是一种熵驱动的自发放热过程。

关键词: 三乙烯二胺, 杂表面活性剂, 表面性能, 热力学参数

Abstract:

Triethylene diamine reacted with n-bromodecodecyl, tetradecane and cetane to obtain monoquaternary ammonium salt, and then reacted with ethyl chloroacetate to obtain a series of novel hetero surfactants（structural formula as BrC_nH₂_n₊₁N（CH₂CH₂）₃NCH₂COO, n=12, 14, 16, named 3a, 3b, 3c） after alkaline hydrolysis and purification, with the total yield of 78.8%, 80.6% and 83.0% （based on triethylene diamine）, respectively. The structure was characterized by NMR, ESI-MS and FT-IR, and their surface properties and thermodynamic parameters were studied. The results showed that at 298.15K, the cmc values of 3a, 3b, 3c are 0.627, 0.576 and 0.502 mmol/L by the conductivity method （the empirical equation is cmc=1.005 3-0.031 25 n）; the γ_cmcvalues are 38.23, 37.83 and 36.65 mN/m by the hanging drop method （the empirical equation is γ_cmc=43.10-0.395 n）; the Krafft points are 6, 10 and 13 ℃, respectively. The temperature adaptation range is wide. The foaming and foam stability are good, in which the initial foam height of 3c is 100 mm and it drops to 61 mm after 30 min. The emulsification time are 260, 348, and 485 s, respectively. The calculation of thermodynamic parameters showed that the formation of micelles is an entropy-driven spontaneous exothermic process.

Key words: triethylene diamine, hetero surfactant, surface properties, thermodynamic parameters

中图分类号:

TQ423

储佳乐,潘忠稳,宣俊,王翰斌. 基于三乙烯二胺新型表面活性剂的合成及性能研究[J]. 日用化学工业, 2021, 51(1): 21-27.

CHU Jia-le,PAN Zhong-wen,XUAN Jun,WANG Han-bin. Synthesis and properties of novel surfactants based on triethylene diamine[J]. China Surfactant Detergent & Cosmetics, 2021, 51(1): 21-27.

图/表 11

图1

图2

图3

图4

图5

图6

表1

表2

图7

表3

表4

参考文献 22

[1]	Liu fan, Xu Hujun. Synjournal and performance of an asymmetric cationic Gemini surfactant[J]. China Surfactant Detergent & Cosmetics, 2016,46(2) : 80-83.
[2]	Wang Hongdi, Ma Jianzhong, Lv Bin, et al. Synjournal and performance of asymmetric Gemini sulfosuccinate surfactant[J]. China Surfactant Detergent & Cosmetics, 2015,45(12) : 685-689.
[3]	Zhang Heng, Mao Jincheng, Zhao Jinzhou, et al. The impact of dissymmetry on the aggregation properties of heterogemini surfactants[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2020,585: 124165-124175. doi: 10.1016/j.colsurfa.2019.124165
[4]	Li Yancheng, Cui Junfu, Hao Zhilian, et al. Application of heterogeneous surfactant injection enhancement technology in low permeability reservoir[J]. Petrochemical Industry Technology, 2019,26(8) : 258-259.
[5]	Xia Yini, Fang Shenwen, Tan Qiuyuan, et al. Synjournal and bactericidal performance assessment of a dissymmetric bis-quaternary ammonium salt surfactant[J]. Speciality Petrochemicals, 2013,30(3) : 5-8.
[6]	Zhang J, Gong L, Song W W, et al. Synjournal of imidazoline-based dissymmetric bis-quaternary ammonium Gemini surfactant and its inhibition mechanism on Q235 steel in hydrochloric acid medium[J]. Materials and Corrosion, 2012,63(7) : 636-645.
[7]	Wang H, Wettig S D. Synjournal and aggregation properties of dissymmetric phytanyl-Gemini surfactants for use as improved DNA transfection vectors[J]. Physical Chemistry Chemical Physics, 2011,13(2) : 637-642. doi: 10.1039/c0cp00146e
[8]	Mao Jincheng, Zhang Heng, Zhang Wenlong, et al. Dissymmetric beauty: A novel design of heterogemini viscoelastic surfactant for the clean fracturing fluid[J]. Journal of Industrial and Engineering Chemistry, 2018,60: 133-142. doi: 10.1016/j.jiec.2017.10.048
[9]	Sun Yazhou. Synthesis of asymmetric cationic surfactants and properties of their mixtures[D]. Dalian: Dalian University of Technology, 2015.
[10]	Feng Yuexia, Yin Ning, Li Qifeng, et al. Synjournal of poly (1, 6-hexanediol) carbonate diols catalyzed by triethylenediamine[J]. Polymer Materials Science & Engineering, 2008,24(5) : 28-31.
[11]	Han Shiyan, Song Zhanqian, Fang Guizhen, et al. Synjournal and analysis of rosin-based quaternary ammonium Gemini surfactant[J]. Chemistry and Industry of Forest Products, 2009,29(S1):110-112.
[12]	Yadollah B, Farhad S, Omid G J. Selective oxidation of sulfides to sulfoxides using novel nano Brnsted dicationic ionic liquid as effective reagent under grinding conditions[J]. Journal of Molecular Liquids, 2018,265: 517-524. doi: 10.1016/j.molliq.2018.06.036
[13]	Shi Yunhai, Chen Qibin, Tong Si, et al. Synjournal and quantitative determination of alkanediyl-α, ω-bis (dimethyl alkylammonium bromide)[J]. Chinese Journal of Analytical Chemistry, 2003,31(3) : 322-325.
[14]	Patra N, Mal A, Dey A, et al. Influence of solvent, electrolytes, β-CD, OTAB on the Krafft temperature and aggregation of sodium tetradecyl sulfate[J]. Journal of Molecular Liquids, 2019,280: 307-313. doi: 10.1016/j.molliq.2019.02.002
[15]	Zeng Xiangchu, Li Xiaorui. Study on the synjournal and properties of gemini quaternary ammonium surfactant[J]. Applied Chemical Industry, 2017,46(2) : 221-224.
[16]	You Y, Wu X, Zhao J, et al. Effect of alkyl tail length of quaternary ammonium Gemini surfactants on foaming properties[J]. Colloids & Surfaces a Physicochemical & Engineering Aspects, 2011,384(3) : 164-171.
[17]	Cserháti T. Alkyl ethoxylated and alkylphenol ethoxylated nonionic surfactants: interaction with bioactive compounds and biological effects[J]. Environmental Health Perspectives, 1995,103(4) : 358-364. doi: 10.1289/ehp.103-1519097 pmid: 7607136
[18]	Zhao Zhe, Wang Qifang. Progress on methods of measuring surface active agent’s critical micelle concentration[J]. Practical Pharmacy and Clinical Remedies, 2010,13(2) : 140-144.
[19]	Chen Geng, Pan Zhongwen, Zhou Yang. Synjournal and properties of Gemini surfactant with isophthalamide[J]. Journal of Anhui University (Natural Science Edition), 2015,39(2) : 81-88.
[20]	Wu X, Dai C, Fang S, et al. The effect of hydroxyl on the solution behavior of a quaternary ammonium Gemini surfactant[J]. Physical Chemistry Chemical Physics, 2017,19(24) : 16047-16056. doi: 10.1039/c7cp00131b pmid: 28597883
[21]	Liu Haiyan, Gu Daming, Liu Guoyu, et al. Synjournal and surface properties of novel gemini imidazolium surfactants[J]. Chemical Journal of Chinese Universities, 2013,34(2) : 401-407.
[22]	Zana R. Dimeric (Gemini) surfactants: Effect of the spacer group on the association behavior in aqueous solution[J]. Journal of Colloid and Interface Science, 2002,248(2) : 203-220. doi: 10.1006/jcis.2001.8104 pmid: 16290524

T/K	cmc/（mmol·L^-1）
T/K	3a	3b	3c
298.15	0.627	0.576	0.502
308.15	0.640	0.588	0.513
318.15	0.646	0.603	0.529
328.15	0.655	0.629	0.557
333.15	0.662	0.638	0.570

表面活性剂	cmc/（mmol·L^-1）	T?S_m^θ/（kJ·mol^-1）	?G_m^θ/（kJ·mol^-1）	?H_m^θ/（kJ·mol^-1）	β
3a	0.627	17.62	-18.76	-1.14	0.526 2
3b	0.576	17.48	-20.13	-2.65	0.588 6
3c	0.502	17.19	-20.30	-3.11	0.578 0

表面活性剂	cmc/（mmol·L^-1）	γ_cmc/（mN·m^-1）
3a	0.630	38.23
3b	0.573	37.83
3c	0.507	36.65
文献^[11]化合物Ⅱ	0.970	43.41

表面活性剂	cmc/（mmol·L^-1）	γ_cmc/（mN·m^-1）	Γ_max/（μmol·m^-2）	A_min/nm²	pc₂₀	π_cmc/（mN·m^-1）
3a	0.630	38.23	2.03	0.82	3.79	32.96
3b	0.573	37.83	1.91	0.87	3.88	34.14
3c	0.507	36.65	1.70	0.98	4.08	35.32