Synthesis and properties of Gemini surfactant containing polyfunctional groups

doi:10.16085/j.issn.1000-6613.2019-1570

Abstract

Abstract:

A series of Gemini surfactant (I₈, I₁₂，I₁₄, I₁₆) containing polyfunctional group were synthesized by using chloroacetyl chloride, isophthaloyl chloride, long alkyl chain primary amine(carbon chain length was 8,12,14,16), and N,N-dimethylethanolamine as main raw materials. The structures of product were characterized by FTIR and ¹H NMR. The critical micelle concentrations (CMC) and the relevant thermodynamic parameters (, , ) were determined at different temperatures by electrical conductivity measurements. The surface tensions (γ_CMC) were determined by surface tension method at 298.15K. The foaming properties and emulsifying properties were investigated. The results show that target products have lower CMC values, and the lowest CMC value reaches 0.05mmol/L at 298.15K. The minimum value of γ_CMC for I₁₆ is 36.14mN/m. Foam properties and emulsification test results show that I₈ exhibits the best foaming ability; I₁₂ and I₁₄ exhibit the best foam stability (100%) at 298.15K. As emulsifying agent for benzene and xylene the target products have good emulsifying properties. Among these products, I₁₂has the best emulsifying properties for xylene, and the emulsification time is 900s; I₁₆ has the best emulsifying properties for benzene, and the emulsification time is 629s.

Key words: polyfunctional surfactant, conductivity, surface tension, foaming properties, emulsifying properties

摘要：

以氯乙酰氯、间苯二甲酰氯、长链伯胺（碳链长度为8、12、14和16）和N,N-二甲基乙醇胺为原料合成了一系列含多官能团Gemini阳离子表面活性剂目标产物（I₈、I₁₂、I₁₄和I₁₆）。采用红外光谱和核磁氢谱对产物进行了结构表征。通过电导率法测量目标产物在不同温度下的临界胶束浓度（CMC），并计算出胶束的热力学参数（、、）；在298.15K条件下，通过表面张力法测定目标产物的表面张力（γ_CMC），并探讨了目标产物的泡沫性能和乳化性能。结果表明：目标产物有较低的临界胶束浓度值（CMC），在298.15K条件下，最低CMC达到0.05mmol/L；I₁₆的γ_CMC最低为36.14mN/m；泡沫性和乳化性测试结果表明，在298.15K条件下，I₈的起泡能力最好，I₁₂和I₁₄的稳泡性最好，均达到100%；目标产物对苯和二甲苯具有很好的乳化性能，其中I₁₂对二甲苯的乳化性能最好，乳化时间为900s，I₁₆对苯的乳化性能最好，乳化时间为629s。

关键词: 多官能团表面活性剂, 电导率, 表面张力, 起泡性能, 乳化性能

CLC Number:

TQ423

Liyan WANG, Jia YANG, Yunqing LI, Li TANG, Jiaqing LIU, Yuying DU, Dingcheng WU. Synthesis and properties of Gemini surfactant containing polyfunctional groups[J]. Chemical Industry and Engineering Progress, 2020, 39(8): 3278-3286.

王丽艳, 杨佳, 李云晴, 唐丽, 刘家庆, 杜昱嬴, 吴定成. 含多官能团Gemini表面活性剂的合成及性能[J]. 化工进展, 2020, 39(8): 3278-3286.

References

1	赖小娟, 汪洁, 王磊, 等. 新型磺酸基Gemini表面活性剂的合成及其在油气井中的应用性能[J]. 化工进展, 2018, 37(5): 1956-1961.
1	LAI X J, WANG J, WANG L, et al. Synthesis of a novel sulfate Gemini surfactant and its application in oilfield[J]. Chemical Industry and Engineering Progress, 2018, 37(5): 1956-1961.
2	蒲春生, 白云, 陈刚. 双子表面活性剂的研究及应用进展[J]. 应用化工, 2019, 48(9): 2203-2207.
2	PU C S, BAI Y, CHEN G. Progresses in research and application of Gemini surfactant[J]. Applied Chemical Industry, 2019, 48(9): 2203-2207.
3	黄茂福. 表面活性剂类及膨润土类防沾污洗涤剂的发展与现状分析[J]. 印染助剂, 2018, 35(7): 6-11.
3	HUANG F M. Development and current situation of surfactant and bentonite anti fouling detergents[J]. Textile Auxiliaries, 2018, 35(7): 6-11.
4	KATARZYNA L, KINGA K. Antimicrobial and cytotoxic properties of bisquaternary ammonium bromides of different spacer length[J]. Journal of Surfactants and Detergents, 2018, 21(1): 91-99.
5	徐艳艳, 刘伟, 舒婷, 等. 泡沫浮选耦合膜过滤回收有机废水中纳米TiO₂光催化剂的工艺[J]. 化工进展, 2019, 38(10): 4773-4779.
5	XU Y Y, LIU W, SHU T, et al. Recovery of nano-sized TiO₂ photocatalyst from its organic wastewater by using a technology of froth flotation coupled with ultrafiltration[J]. Chemical Industry and Engineering Progress, 2019, 38(10): 4773-4779.
6	El-SHARAKY E S, El-TABEY A E, El-DIN M R N, et al. Polyoxyethylene alkenyl succinate Gemini emulsifier for diesel fuel nanoemulsion[J]. Energy & Fuels, 2019, 33(6), 5476-5487.
7	潘一, 王瞳煜, 杨双春, 等. 黏弹性表面活性剂压裂液的研究与应用进展[J]. 化工进展, 2018, 37(4): 1566-1574.
7	PAN Y, WANG T Y, YANG S C, et al. Progress in research and application of viscoelastic surfactant fracturing fluid[J]. Chemical Industry and Engineering Progress, 2018, 37(4): 1566-1574.
8	郭辉, 庄玉伟, 褚艳红, 等. 双子表面活性剂类清洁压裂液的研究进展[J]. 化工进展, 2018, 37(8): 3155-3163.
8	GUO H, ZHUANG Y W, CHU Y H, et al. Research progress in Gemini surfactant clean fracturing fluids[J]. Chemical Industry and Engineering Progress, 2018, 37(8): 3155-3163.
9	QIANG Y, ZHANG S, TAN B, et al. Evaluation of Ginkgo leaf extract as an eco-friendly corrosion inhibitor of X70 steel in HCl solution[J]. Corrosion Science, 2018, 133: 6-16.
10	王艳娥, 张子安, 唐爱星, 等. 表面活性剂改性磁性氧化石墨烯共价固定脂肪酶CRL[J]. 化工进展, 2019, 38(9): 4255-4263.
10	WANG Y E, ZHANG Z A, TANG A X, et al. Surfactant modified magnetic graphene oxide covalent immobilized candida rugose lipase[J]. Chemical Industry and Engineering Progress, 2019, 38(9): 4255-4263.
11	AKBAS H, KOCAOGLU S, BOZ M, et al. A novel cationic Gemini surfactant with amide group: synthesis and micellization behavior in aqueous solutions[J]. Colloid & Polymer Science, 2016, 294(9): 1439-1451.
12	ZHANG Q, GAO Z N, FENG X, et al. Surface tension and aggregation properties of novel cationic Gemini surfactants with diethylammonium headgroups and diamido spacer[J]. Langmuir, 2012, 28(33): 11979-11987.
13	HU D H, GUO X F, JIA L H. Synthesis, surface active properties of novel Gemini surfactants with amide groups and rigid spacers[J]. Journal of Surfactants & Detergents, 2013, 16(6): 913-919.
14	YANG C P, SONG Z Z, ZHAO J J, et al. Self-assembly properties of ultra-long-chain gemini surfactants bearing multiple amide groups with high performance in fracturing fluid application[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2017, 523:62-70.
15	TAWFIK S M. Synthesis, surface, biological activity and mixed micellar phase properties of some biodegradable Gemini cationic surfactants containing oxycarbonyl groups in the lipophilic part[J]. Journal of Industrial and Engineering Chemistry, 2015, 28: 171-183.
16	WANG L Y, ZHANG Y, DING L M, et al. Synthesis and physiochemical properties of novel Gemini surfactants with phenyl-1,4-bis(carbamoylmethyl) spacer[J]. RSC Advances, 2015, 5(91): 74764-74773.
17	CHAI J L, ZHANG H M, LIU N, et al. Comparison between phase behavior of Gemini imidazoliums and monomeric ionic liquid surfactants in W/O microemulsion systems[J]. Journal of Dispersion Science & Technology, 2014, 36(1): 477-483.
18	KAMBOJ R, BHARMORIA P, CHAUHAN V, et al. Micellization behavior of morpholinium-based amide-functionalized ionic liquids in aqueous media[J]. Langmuir, 2014, 30(33): 9920-9930.
19	SRISHTI S, TIKARIHA D, LAKRA J, et al. Effect of polar organic solvents on self-aggregation of some cationic monomeric and dimeric surfactants[J]. Journal of Surfactants & Detergents, 2015, 18(4): 629-640.
20	王丽艳, 闫铁, 秦洪磊, 等. 酰胺键为间隔基的吡啶双子表面活性剂合成及性能[J]. 化工进展, 2015, 34(11): 4026-4029.
20	WANG L Y, YAN T, QIN H L, et al. Synthesis and properties of pyridine Gemini surfactants containing amide spacer[J]. Chemical Industry and Engineering Progress, 2015, 34(11): 4026-4029.
21	谢益诚, 许虎君, 刘佳佳, 等. 含哌啶环的阳离子双子表面活性剂的合成及性能研究[J]. 日用化学工业, 2017, 47(4): 181-185.
21	XIE Y C, XU H J, LIU J J, et al. Synthesis and properties of cationic Gemini surfactant containing bis-piperidinium group[J]. China Surfactant Detergent & Cosmetics, 2017, 47(4): 181-185.
22	GARCIA M T, RIBOSA I, PEREZ L, et al. Aggregation behavior and antimicrobial activity of ester functionalized imidazolium and pyridinium-based ionic liquids in aqueous solution[J]. Langmuir, 2013, 29(3): 2536-2545.
23	KAMBOJ R, SINGH S, BHADANI A, et al. Gemini imidazolium surfactants: synthesis and their biophysiochemical study[J]. Langmuir, 2012, 28(33): 11969-11978.
24	梁维平, 赵晓辉, 安东, 等. 四硅氧烷Gemini咪唑表面活性剂的合成及表面性能[J]. 高等学校化学学报, 2015, 36(10): 2009-2015.
24	LIANG W P, ZHAO X H, AN D, et al. Synthesis and surface properties of siloxane Gemini imidazolium surfactant[J]. Chemical Journal of Chinese Universities, 2015, 36(10): 2009-2015.
25	AHMAD I, PATIAL P, KAUR C, et al. Cationic imidazolium monomeric surfactants: their synthesis and surface active properties[J]. Journal of Surfactants & Detergents, 2014, 17(2): 269-277.
26	穆瑞花, 赖小娟, 王磊, 等. 磺基甜菜碱Gemini表面活性剂的合成与应用性能[J]. 化工进展, 2019, 38(7): 3377-3383.
26	MU R H, LAI X J, WANG L, et al. Synthesis and application properties of a sulfobetaine Gemini surfactant[J]. Chemical Industry and Engineering Progress, 2019, 38(7): 3377-3383.
27	LU T, LAN Y, LIU C, et al. Surface properties, aggregation behavior and micellization thermodynamics of a class of Gemini surfactants with ethyl ammonium headgroups[J]. Journal of Colloid and Interface Science, 2012, 377(1): 222-230.
28	刘海燕, 顾大明, 刘国宇, 等. 新型Gemini咪唑表面活性剂的合成及表面性能[J]. 高等学校化学学报, 2013, 34(2): 401-407.
28	LIU H Y, GU D M, LIU G Y, et al. Synthesis and surface properties of novel Gemini imidazole surfactants[J]. Chemical Journal of Chinese Universities, 2013, 34(2): 401-407.
29	金礼俊, 唐善法, 崔琰奇, 等. N,N'-双棕榈酰基对苯二胺二乙基磺酸钠的合成及性能[J]. 精细化工, 2019, 36(3): 437-441.
29	JIN L J, TANG S F, CUI Y Q, et al. Synthesis and properties of N, N'-dipalmitoyl p-phenylenediamine diethyl sulfonate[J]. Fine Chemicals, 2019, 36(3): 437-448.

[1]	ZHANG Hongming, LU Jiongyuan, WANG Sanfan. Research progress on molecular structure of anion exchange membrane for fuel cells [J]. Chemical Industry and Engineering Progress, 2022, 41(S1): 318-330.
[2]	GUO Rui, LI Ping’an, ZHAO Yunfei. Synthesis and performance of silicon modified BPA-PA phenolic epoxy resin conductive adhesive [J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4473-4480.
[3]	YANG Yukai, XIA Yongpeng, XU Fen, SUN Lixian, GUAN Yanxun, LIAO Lumin, LI Yaying, ZHOU Tianhao, LAO Jianhao, WANG Yu, WANG Yingjing. Research progress of erythritol phase change materials for thermal storage [J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4357-4366.
[4]	KUAI Zihan, YAN Ting, WU Shaofei, ZHOU Yuxiang, PAN Weiguo. Fabrication and heat storage properties of stearyl alcohol/expanded graphite composite phase change materials [J]. Chemical Industry and Engineering Progress, 2021, 40(S1): 301-310.
[5]	MA Mingyan, ZHAI Yuling, XUAN Zihao, ZHOU Shuguang, LI Zhixiang. Stability and thermal performance of ternary hybrid nanofluids [J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4179-4186.
[6]	XU Zhong, HOU Jing, WU Enhui, LI Jun, HUANG Ping, TANG Yalan. Effect of graphite on latent heat and conductivity of activated carbon/fatty acid composite phase change materials [J]. Chemical Industry and Engineering Progress, 2021, 40(7): 3878-3891.
[7]	LIU Zheng, LIU Ran, HUA Er, JI Jianlong. Water effects on physicochemical properties of protic ionic liquid with N-hexylamine as cation and bis(trifluoromethylsulfonyl) imide as anion [J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2270-2277.
[8]	ZHOU Sili, ZHANG Zhengguo, FANG Xiaoming. Research progress of solid-solid phase change materials for thermal energy storage [J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1371-1383.
[9]	Guomin MIAO, Haiyan LEI, Chuanshan DAI, Fei MA. Natural convection heat transfer characteristics of coupled surface tension outside the tube in a closed cavity [J]. Chemical Industry and Engineering Progress, 2020, 39(S2): 26-35.
[10]	Lingyun KONG, Xiujie QUAN, Chaobo LI, Miao YU. Molecular simulation and experimental demonstration of adsorption behavior of emulsifier on surface of chemical composition of aggregate [J]. Chemical Industry and Engineering Progress, 2020, 39(8): 3196-3204.
[11]	Xiaohua LI,Zichun YANG,Kunfeng LI,Shuang ZHAO,Zhifang FEI,Zhen ZHANG. Preparation and characterization of transparent and compressible methylsilsesquioxane aerogels using MTES as precursor [J]. Chemical Industry and Engineering Progress, 2020, 39(3): 1115-1121.
[12]	Xiang WANG,Xuelai ZHANG,Weisan HUA,Lingyu ZHENG,Lu LIU,Caimei YU. Preparation and thermal properties of Na₂HPO₄·12H₂O composite phase change material for thermal energy storage [J]. Chemical Industry and Engineering Progress, 2019, 38(12): 5457-5464.
[13]	Yuling ZHAI,Jiang WANG,Long LI,Mingyan MA,Peitao YAO. Evaluation and effect of mixture ratio on heat transfer performance of Al₂O₃/water nanofluids [J]. Chemical Industry and Engineering Progress, 2019, 38(11): 4865-4872.
[14]	Qiuhui YAN, Xiaoyang SUN, Jieren LUO, Zhiju WU, Cong ZHOU. Experimental study on improving the performance of rock wool and glass wool by silica aerogel [J]. Chemical Industry and Engineering Progress, 2019, 38(06): 2847-2853.
[15]	Qingjun GU, Hua FEI, Linya WANG, Min FANG, Dahua JIANG. Research progress on thermal properties of fatty acid phase change energy storage materials [J]. Chemical Industry and Engineering Progress, 2019, 38(06): 2825-2834.