双酰胺基Gemini阳离子表面活性剂的合成及应用性能
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摘要
以月桂酸、N, N-二甲基-1, 3-丙二胺和1, 3-二氯-2-丙醇为原料,在碳酸钠催化下合成了双酰胺基Gemini阳离子表面活性剂(ADQ-12)。通过FTIR和1HNMR对其结构进行了表征,并对其表/界面活性、抗静电性、抗盐性、抑菌性以及生物降解性能进行了测定。结果表明,25℃下,ADQ-12具有比传统单链阳离子表面活性剂低1～2个数量级的临界胶束浓度(CMC为1.41×10-4mol/L),表面张力(γCMC)为32.26mN/m;在ADQ-12质量浓度为0.05 g/L时,煤油/水界面张力(IFT)可降低至超低界面水平(4.1×10-3 mN/m),远低于十六烷基三甲基溴化铵(CTAB)的2.0mN/m;在质量浓度为1.0g/L时,ADQ-12对二价钙、镁离子具有优良的耐盐性能(>60 g/L);ADQ-12即使在低质量浓度下(10 mg/L)对金黄色葡萄球菌和大肠杆菌的抑菌率仍达到100%,相比双癸基二甲基氯化铵(DDAC), ADQ-12的抑菌能力更强;ADQ-12的7 d生物降解度能达到99%,表现出优异的生物降解性能。
A Gemini cationic surfactant with diamide groups(ADQ-12) was synthesized using lauric acid,N,N-dimethyl-1,3-propanediamine and 1,3-dichloro-2-propanol as raw materials in the presence of a catalytic amount of sodium carbonate.The structure was characterized by FTIR and 1 HNMR.The surface/interfacial activity,antistatic property,salt resistance,antibacterial activity and biodegradation were measured.The results showed that ADQ-12 has a critical micelle concentration(CMC) value of 1.41×10-4 mol/L,which is 1～2 orders of magnitude lower than conventional single cationic surfactants with a surface tension γCMC of 32.26 m N/m.When the mass concentration of ADQ-12 is 0.05 g/L,the interfacial tension of kerosene/water(IFT) could be reduced to ultra-low level(4.1×10-3 m N/m),far lower than that of hexadecyl trimethyl ammonium bromide(CTAB)(2.0 m N/m).At a mass concentration of 1.0 g/L,ADQ-12 exhibits strong resistance to calcium and magnesium ions(>60 g/L).The inhibition rates of ADQ-12 against S.aureus and E.coli are still 100% even at a low mass concentration(10 mg/L),and the antibacterial activity of ADQ-12 is higher than that of didecyl dimethyl ammonium chloride(DDAC).In addition,ADQ-12 demonstrates excellent biodegradability,its biodegradation after 7 days is 99%.
A Gemini cationic surfactant with diamide groups(ADQ-12) was synthesized using lauric acid,N,N-dimethyl-1,3-propanediamine and 1,3-dichloro-2-propanol as raw materials in the presence of a catalytic amount of sodium carbonate.The structure was characterized by FTIR and 1 HNMR.The surface/interfacial activity,antistatic property,salt resistance,antibacterial activity and biodegradation were measured.The results showed that ADQ-12 has a critical micelle concentration(CMC) value of 1.41×10-4 mol/L,which is 1～2 orders of magnitude lower than conventional single cationic surfactants with a surface tension γCMC of 32.26 m N/m.When the mass concentration of ADQ-12 is 0.05 g/L,the interfacial tension of kerosene/water(IFT) could be reduced to ultra-low level(4.1×10-3 m N/m),far lower than that of hexadecyl trimethyl ammonium bromide(CTAB)(2.0 m N/m).At a mass concentration of 1.0 g/L,ADQ-12 exhibits strong resistance to calcium and magnesium ions(>60 g/L).The inhibition rates of ADQ-12 against S.aureus and E.coli are still 100% even at a low mass concentration(10 mg/L),and the antibacterial activity of ADQ-12 is higher than that of didecyl dimethyl ammonium chloride(DDAC).In addition,ADQ-12 demonstrates excellent biodegradability,its biodegradation after 7 days is 99%.
引文
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[23]Ju H B,Jiang Y J,Geng T,et al.Equilibrium and dynamic surface tension of quaternary ammonium salts with different hydrocarbon chain length of counterions[J].Journal of Molecular Liquids,2017,225:606-612.
[24]Chen H,Han L,Luo P,et al.The interfacial tension between oil and Gemini surfactant solution[J].Surface Science,2004,552(1/2/3):53-57.
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[2]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(1):164-171.
[3]Kamal M S.A review of Gemini surfactants:potential application in enhanced oil recovery[J].Journal of Surfactants&Detergents,2016,19(2):223-236.
[4]Zhang Q,Gao Z,Xu F,et al.Surface tension and aggregation properties of novel cationic Gemini surfactants with diethylammonium headgroups and a diamido spacer[J].Langmuir,2012,28(33):11979-11987.
[5]Ghumare A K,Pawar B V,Bhagwat S S.Synthesis and antibacterial activity of novel amido-amine-based cationic Gemini surfactants[J].Journal of Surfactants&Detergents,2013,16(1):85-93.
[6]Chang H H,Wang Y,Cui Y,et al.Equilibrium and dynamic surface tension properties of Gemini quaternary ammonium salt surfactants with hydroxyl[J].Colloids&Surfaces a Physicochemical&Engineering Aspects,2016,500:230-238.
[7]Yu Pengming(余鹏鸣),Zhang Wei(张威),Wang Fengshou(王丰收),et al.Properties of a series of bis(quaternary ammonium)Gemini surfactant with 2-hydroxypropyl group as spacer[J].China Surfactant Detergent&Cosmetics(日用化学工业),2015,45(6):319-322.
[8]Guo Rui(郭睿),Li Huanle(李欢乐),Yang Jiangyue(杨江月),et al.Preparation and properties of series of m-3(OH)-m type surfactant[J].Fine Chemicals(精细化工),2016,33(5):514-518.
[9]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&Engineering Chemistry,2015,28:171-183.
[10]Qin Yong(秦勇),Zhang Gaoyong(张高勇),Kang Baoan(康保安).The relationship between the structure of surfactant and biodegradability[J].Detergent&Cosmetics(日用化学品科学),2002,25(5):20-23.
[11]Chen Fengsheng(陈凤生),Liu Xuemin(刘学民),Hu Zengrong(胡增荣),et al.Synthesis and properties of cationic Gemini surfactants with amide group[J].China Surfactant Detergent&Cosmetics(日用化学工业),2008,38(5):285-288.
[12]National Committee on the Standardization of Surfactants and Detergents(全国表面活性剂和洗涤用品标准化技术委员会).Test methods for industrial stearic acids:GB/T 9104-2008[S].Beijing:China Standard Publishing House(中国标准出版社),2008:3-4.
[13]National Committee on the Standardization of Surfactants and Detergents(全国表面活性剂和洗涤用品标准化技术委员会).Surface active agents-detergents-determination of cationic-active matter content:GB/T 5174-2004[S].Beijing:China Standard Publishing House(中国标准出版社),2004:1-3.
[14]National Committee on the Standardization of Surfactants and Detergents(全国表面活性剂和洗涤用品标准化技术委员会).Detergents:Ring up liquid film method to measure surface tension:QB/T 1323-1991[S].Beijing:China Standard Publishing House(中国标准出版社),1991:334-344.
[15]Jiang Y,Geng T,Li Q,et al.Equilibrium and dynamic surface tension properties of salt-free catonic surfactants with different hydrocarbon chain lengths[J].Journal of Molecular Liquids,2015,204:126-131.
[16]National Committee on the Standardization of Surfactants and Detergents(全国表面活性剂和洗涤用品标准化技术委员会).Determination of antistatic performance for fabric conditioners:GB/T 16801-2013[S].Beijing:China Standard Publishing House(中国标准出版社),2013:1-5.
[17]National Committee on the Standardization of Surfactants and Detergents(全国表面活性剂和洗涤用品标准化技术委员会).Surface active agents-determination of stability in hard water:GB/T 7381-2010[S].Beijing:China Standard Publishing House(中国标准出版社),2010:1-3.
[18]National Committee on the Standardization of Surfactants and Detergents(全国表面活性剂和洗涤用品标准化技术委员会).Test methods for evaluating daily chemical products in antibacterial and bacteriostatic efficacy:QB/T2738-2012[S].Beijing:China Standard Publishing House(中国标准出版社),2012:1-22.
[19]National Committee on the Standardization of Surfactants and Detergents(全国表面活性剂和洗涤用品标准化技术委员会).Test method for biodegradability of surfactants:GB/T 15818-2006[S].Beijing:China Standard Publishing House(中国标准出版社),2006:8-9.
[20]Zhao Guoxi(赵国玺),Zhu Buyao(朱?瑶).Principles of Surfactant Action[M].Beijing:China Light industry Press House(中国轻工业出版社),2003:253-257.
[21]Li Gangsen(李刚森),Zhao linxiu(赵林秀),Wang Peiyi(王培义),et al.Synthesis and surface activity of cationic Gemini surfactant N,N'-bis(octadecyl/tetradecyl dimethyl)-1,2-dichloro-1,4-benzene dimethyl ammonium salt[J].Fine Chemicals(精细化工),2016,33(5):519-524.
[22]Gao X,Wang Y,Zhao X,et al.Equilibrium and dynamic surface tension properties of Gemini quaternary ammonium salt surfactants with ester groups[J].Colloids&Surfaces a Physicochemical&Engineering Aspects,2016,509:130-139.
[23]Ju H B,Jiang Y J,Geng T,et al.Equilibrium and dynamic surface tension of quaternary ammonium salts with different hydrocarbon chain length of counterions[J].Journal of Molecular Liquids,2017,225:606-612.
[24]Chen H,Han L,Luo P,et al.The interfacial tension between oil and Gemini surfactant solution[J].Surface Science,2004,552(1/2/3):53-57.
[25]Bera A,Mandal A,Guha B B.Synergistic effect of surfactant and salt mixture on interfacial tension reduction between crude oil and water in enhanced oil recovery[J].Journal of Chemical&Engineering Data,2014,59(1):89-96.
[26]National Committee on the Standardization of Surfactants and Detergents(全国表面活性剂和洗涤用品标准化技术委员会).Fabric softening agent:QB/T 4535-2013[S].Beijing:China Standard Publishing House(中国标准出版社),2013:1-3.
[27]Tang Weiyue(唐伟月),Geng Tao(耿涛),Jiang Yajie(姜亚洁),et al.Properties of several dodecyl quaternary ammonium salts with noval counterions[J].Fine Chemicals(精细化工),2015,32(10):1106-1111.