一类以对苯二胺为联接基的双子表面活性剂的合成及性能
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摘要
以环氧氯丙烷,对苯二胺和N,N-二甲基烷基胺为原料,分两步合成了一系列具有不同疏水链长的新型双子表面活性剂C_(12)、C_(16)和C_(18),通过FT-IR和~1H NMR对产物结构进行表征,测定了苯二胺型表面活性剂的临界胶束浓度(cmc)和表面张力(γ_(cmc))以及Krafft点、乳化、泡沫和抗菌性能。结果表明,在25 ℃时C_(12)、C_(16)和C_(18)的cmc分别为3.29×10~(-3), 2.53×10~(-4)和3.14×10~(-4) mol/L,(γ_(cmc))分别为28.24,31.95和35.06 mN/m;C_(12)和C_(16)的Krafft点均小于0 ℃,C18的Krafft点为10 ℃;C12的发泡性优于C_(16)和C_(18);C_(18)的乳化性能强于C12和C16;C_(12)、C_(16)和C_(18)均具有优异的抗微生物活性。
A series of novel Gemini surfactants C_(12), C_(16), and C_(18_ with the hydrophobic groups of different lengths were synthesized with epichlorohydrin, N, N-dimethylalkyl amine and p-phenylenediamine as materials in two steps. The products were characterized by FT-IR and ~1H NMR. The critical micelle concentration(cmc)and the corresponding surface tension((γ_(cmc)))of the phenylenediamine surfactants in aqueous solution were measured at 25 ℃ by surface tensiometer. The Krafft points and the emulsifying, foaming and antimicrobial properties of the aqueous solutions were also determined. The results show that the cmc of C_(12)、C_(16) and C_(18) at 25 ℃ are 3.29×10~(-3), 2.53×10~(-4) and 3.14×10~(-4) mol/L, respectively, and the (γ_(cmc)) are 28.24, 31.95 and 35.06 mN/m, respectively. The Krafft points of C_(12) and C_(16) are both below 0 ℃, and the Krafft point of C_(18) is 10 ℃. The foaming properties of C_(12) are better than those of C_(16) and C_(18). The emulsifying properties of C_(18) are better than those of C_(12) and C_(16). C_(12)、C_(16) and C_(18) have shown excellent antimicrobial activities.
A series of novel Gemini surfactants C_(12), C_(16), and C_(18_ with the hydrophobic groups of different lengths were synthesized with epichlorohydrin, N, N-dimethylalkyl amine and p-phenylenediamine as materials in two steps. The products were characterized by FT-IR and ~1H NMR. The critical micelle concentration(cmc)and the corresponding surface tension((γ_(cmc)))of the phenylenediamine surfactants in aqueous solution were measured at 25 ℃ by surface tensiometer. The Krafft points and the emulsifying, foaming and antimicrobial properties of the aqueous solutions were also determined. The results show that the cmc of C_(12)、C_(16) and C_(18) at 25 ℃ are 3.29×10~(-3), 2.53×10~(-4) and 3.14×10~(-4) mol/L, respectively, and the (γ_(cmc)) are 28.24, 31.95 and 35.06 mN/m, respectively. The Krafft points of C_(12) and C_(16) are both below 0 ℃, and the Krafft point of C_(18) is 10 ℃. The foaming properties of C_(12) are better than those of C_(16) and C_(18). The emulsifying properties of C_(18) are better than those of C_(12) and C_(16). C_(12)、C_(16) and C_(18) have shown excellent antimicrobial activities.
引文
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[2]Zhou H T,Liang Y P,Huang P,et al.Systematic investigation of ionic liquid-type gemini surfactants and their abnormal salt effects on the interfacial tension of a water/model oil system[J].Journal of Molecular Liquids,2018,249:33-39.
[3]Zhao W W,Song K,Chen Y,et al.Aggregation of a cationic gemini surfactant with a chelating molecule and effects from calcium ions[J].Langmuir,2017,33(44):12719-12728.
[4]Menger F M,Keiper J S.Gemini surfactants[J].Angewandte Chemie,International Edition,2000,39(11):1907-1920.
[5]Song D D,Sun X L,Liu F Y,et al.Preparation and properties of a sulfonic acid series gemini surfactants[J].China Surfactant Detergent&Cosmetics,2012,42(6):428-431.
[6]Colomer A,Pinazo A,Manresa M A,et al.Cationic surfactants derived from lysine:effects of their structure and charge type on antimicrobial and hemolytic activities[J].Journal of Medicinal Chemistry,2011,54(4):989-1002.
[7]Mondal M H,Malik S,Roy A,et al.Modernization of surfactant chemistry in the age of gemini and bio-surfactants:a review[J].RSC Advances,2015,5(112):92707-92718.
[8]Gao N,Li G R,Chen X D.Progress in field of research work with respect to synthesis and applications of Gemini surfactants[J].China Surfactant Detergent&Cosmetics,2014,44(11):644-651.
[9]Zana R,Benrraou M,Rueff R.Alkanediyl-α,w-bis(dimethylalkylammonium bromide)Surfactants.1.Effect of the spacer chain length on the critical micelle concentration and micelle ionization degree[J].Langmuir,1991,7(6):1072-1075.
[10]Laschewsky A,Lunkenheimer K,Rakotoaly R H,et al.Spacer effects in dimeric cationic surfactants[J].Colloid and Polymer Science,2005,283(5):469-479.
[11]Wang L Y,Zhang Y,Deng Q G,et al.Study on synthesis of aniline surfactants[J].Chemical World,2017(7):424-427.
[12]Rosen M J,Song L D.Surface properties,micellization,and premicellar aggregation of gemini surfactants with rigid and flexible spacers[J].Langmuir,1996,12(5):1149-1153.
[13]Zhu Q,Yang H,Li Y Y,et al.HP-DO3A-based amphiphilic MRIcontrast agents and relaxation enhancement through their assembly with polyelectrolytes[J].Journal of Materials Chemistry B:Materials for Biology and Medicine,2016,4(45):7241-7248.
[14]Lu J F,Wang H G,Liu D,et al.Synthesis of dissymmetric Gemini quaternary ammonium salts cationic asphalt emulsifiers[J].Industrial Catalysis,2006,14(6):62-64.
[15]Gottlieb H E,Kotlya V,Nudelman A.NMR chemical shifts of common laboratory solvents as trace impurities[J].Journal of Organic Chemistry,1997,62(21):7512-7515.
[16]Niu R X,Wang C,Sun Z G,et al.A novel alkyl sulphobetaine gemini surfactant based on striazine:synthesis and properties[J].Journal of Surfactants and Detergents,2017,20(6):1255-1262.
[17]Kang P,Xu H J.Synthesis and properties of dissymmetric gemini surfactants[J].Journal of Surfactants and Detergents,2013,16(6):921-925.
[18]Liu Z T,Ge Y F,Zhang Q,et al.Adsorption and micellization of gemini surfactants with diethylammonium headgroups:effect of the spacer rigidity[J].Journal of Surfactants and Detergents,2017,20(4):765-775.