含三嗪环磺酸盐Gemini表面活性剂的合成及其性能研究
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摘要
Gemini表面活性剂是将两个两亲成分在其头基或靠近头基处通过化学键连接在一起的新型表面活性剂。与传统表面活性剂相比,它具有更高的表面活性,良好的水溶性,更低的Krafft点,独特的流变性能,良好的钙皂分散能力,以及良好的复配协同效应等,在乳化、洗涤、增容等方面有广阔的应用前景。
本文以三聚氯氰、脂肪胺(正己胺、正辛胺、十二胺、十四胺)、氨基乙磺酸以及乙二胺、1,3-丙二胺为原料,通过三步取代反应合成了8种含三嗪环的磺酸盐Gemini表面活性剂,C_m-s-C_m (m=6,8,12,14; s=2,3),采用IR、~1H NMR、~(13)C NMR、ESI-MS对目标产物的结构进行了表征,并详细考察了该类表面活性剂的表面活性及应用性能。
分别采用表面张力法和电导率法测定其CMC。系列产品C_m-2-C_m、C_m-3-C_m的CMC均随着疏水烷基链长度的增加而减小,到C_(12)-2-C_(12),C_(12)-3-C_(12)(实际疏水基碳原子数为14)达到最小值,其CMC值分别为3.34×10~(-5) mol L~(-1)和7.23×10~(-5) mol L~(-1),当实际疏水基碳原子数增加到16时CMC有所增加。同传统单烷基离子型表面活性剂十二烷基硫酸钠(SDS)相比,该类表面活性剂的CMC值低至1~2个数量级,显示出很高的表面活性。此外,表面张力测试结果表明,两系列产品的γcmc随着疏水烷基链长度的增加呈现先减小后增大的趋势,最低γ_(cmc)为33.57 mN/m。
根据质量作用模型,计算了胶束形成自由能以及表面吸附吉布斯自由能。结果表明,表面活性剂胶束的形成过程和表面吸附过程均是自发进行的,且在气液界面吸附的趋势强于在水溶液内部形成胶束的趋势。
对该类表面活性剂进行应用性能测试,随着烷基链长度的增加,其润湿力和钙皂分散力减弱,而乳化力逐渐增强。其中表面活性剂C6-s-C6和C8-s-C8均表现出较好的润湿性和钙皂分散性,适宜作为分散剂使用。
Gemini surfactants represent a new class of surfactants, which is made up of two amphiphilic moieties covalently connected at the level of the head groups or very close to the head groups by a spacer group. Compared with traditional surfactants, Gemini surfactants have higher surface activity, better water solubility, much lower Krafft temperatures, unique rheology behavior, lime soap dispersing property and interaction with traditional surfactants. So they have bright application foreground in the emulsion, washing, solubilization and other industrial fields.
Eight s-triazine sulfonate gemini surfactants, C_m-s-C_m (m=6,8,12,14; s=2,3), were synthesized from cyanuric chloride, aliphatic amine, taurine, ethylenediamine and 1,3-propanediamine. The chemical structures of the prepared compounds were confirmed by 1H NMR, 13C NMR, IR spectra and ESI-MS. In addition, their surface activity and applied properties were studied.
Their critical micelle concentrations (CMC) in the aqueous solutions at 25-5 were determined by surface tension and electrical conductivity methods. With the increasing length of the carbon chain, the values of their CMC initially decreased and then reached a minimum (respectively 3.34×10~(-5)℃mol L~(-1) and 7.23×10~(-5) mol L~(-1) when the carbon number was 14, but increased with the carbon number of 16. The values of CMC of Gemini surfactants C_m-s-C_m are about one or two orders of magnitude lower than that of the monomeric surfactant sodium dodecyl sulfate. Results showed that Gemini surfactants have much higher surface activity than traditional ionic surfactants. In addition, with the increasing length of the carbon chain, the values of theirγ_(cmc) increased at first and then decreased. The minimum value is 33.57 mN/m.
The standard free energy micellization and adsorption (ΔG_(mic)°andΔG_(ads)°) were calculated according to the mass action model. The results indicated that the anionic Gemini surfactants have great ability to form micelles in solution and to adsorb at the air–water interface, and the adsorption is promoted more than the micellization. Meanwhile, the properties for application of the C_m-s-C_m were also investigated. The wetting ability and lime soap dispersing power of C_m-s-C_m decreased with the increasing length of the carbon chain, while the emulsification stability were rising gradually. The C_6-s-C_6 and C_8-s-C_8 possess better wetting ability and lime soap dispersing power. They are suitable for use as dispersants.
本文以三聚氯氰、脂肪胺(正己胺、正辛胺、十二胺、十四胺)、氨基乙磺酸以及乙二胺、1,3-丙二胺为原料,通过三步取代反应合成了8种含三嗪环的磺酸盐Gemini表面活性剂,C_m-s-C_m (m=6,8,12,14; s=2,3),采用IR、~1H NMR、~(13)C NMR、ESI-MS对目标产物的结构进行了表征,并详细考察了该类表面活性剂的表面活性及应用性能。
分别采用表面张力法和电导率法测定其CMC。系列产品C_m-2-C_m、C_m-3-C_m的CMC均随着疏水烷基链长度的增加而减小,到C_(12)-2-C_(12),C_(12)-3-C_(12)(实际疏水基碳原子数为14)达到最小值,其CMC值分别为3.34×10~(-5) mol L~(-1)和7.23×10~(-5) mol L~(-1),当实际疏水基碳原子数增加到16时CMC有所增加。同传统单烷基离子型表面活性剂十二烷基硫酸钠(SDS)相比,该类表面活性剂的CMC值低至1~2个数量级,显示出很高的表面活性。此外,表面张力测试结果表明,两系列产品的γcmc随着疏水烷基链长度的增加呈现先减小后增大的趋势,最低γ_(cmc)为33.57 mN/m。
根据质量作用模型,计算了胶束形成自由能以及表面吸附吉布斯自由能。结果表明,表面活性剂胶束的形成过程和表面吸附过程均是自发进行的,且在气液界面吸附的趋势强于在水溶液内部形成胶束的趋势。
对该类表面活性剂进行应用性能测试,随着烷基链长度的增加,其润湿力和钙皂分散力减弱,而乳化力逐渐增强。其中表面活性剂C6-s-C6和C8-s-C8均表现出较好的润湿性和钙皂分散性,适宜作为分散剂使用。
Gemini surfactants represent a new class of surfactants, which is made up of two amphiphilic moieties covalently connected at the level of the head groups or very close to the head groups by a spacer group. Compared with traditional surfactants, Gemini surfactants have higher surface activity, better water solubility, much lower Krafft temperatures, unique rheology behavior, lime soap dispersing property and interaction with traditional surfactants. So they have bright application foreground in the emulsion, washing, solubilization and other industrial fields.
Eight s-triazine sulfonate gemini surfactants, C_m-s-C_m (m=6,8,12,14; s=2,3), were synthesized from cyanuric chloride, aliphatic amine, taurine, ethylenediamine and 1,3-propanediamine. The chemical structures of the prepared compounds were confirmed by 1H NMR, 13C NMR, IR spectra and ESI-MS. In addition, their surface activity and applied properties were studied.
Their critical micelle concentrations (CMC) in the aqueous solutions at 25-5 were determined by surface tension and electrical conductivity methods. With the increasing length of the carbon chain, the values of their CMC initially decreased and then reached a minimum (respectively 3.34×10~(-5)℃mol L~(-1) and 7.23×10~(-5) mol L~(-1) when the carbon number was 14, but increased with the carbon number of 16. The values of CMC of Gemini surfactants C_m-s-C_m are about one or two orders of magnitude lower than that of the monomeric surfactant sodium dodecyl sulfate. Results showed that Gemini surfactants have much higher surface activity than traditional ionic surfactants. In addition, with the increasing length of the carbon chain, the values of theirγ_(cmc) increased at first and then decreased. The minimum value is 33.57 mN/m.
The standard free energy micellization and adsorption (ΔG_(mic)°andΔG_(ads)°) were calculated according to the mass action model. The results indicated that the anionic Gemini surfactants have great ability to form micelles in solution and to adsorb at the air–water interface, and the adsorption is promoted more than the micellization. Meanwhile, the properties for application of the C_m-s-C_m were also investigated. The wetting ability and lime soap dispersing power of C_m-s-C_m decreased with the increasing length of the carbon chain, while the emulsification stability were rising gradually. The C_6-s-C_6 and C_8-s-C_8 possess better wetting ability and lime soap dispersing power. They are suitable for use as dispersants.
引文
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[2] Zana R. Micellization of amphiphiles: selected aspects[J]. Colloids and Surface A: Physicochemical and Engineering Aspect, 1997, 123-124.
[3]赵剑曦.低聚表面活性剂——从分子结构水平上调控有序聚集体[J].日用化学工业,2002,32.3:39-42.
[4] Zana R, Talmon Y. Dependence of aggregate morphology on structure of dimeric surfactants[J]. NATURE, 1993, 362: 228-230.
[5] Rosen M J. Geminis: a new generation of surfactants[J]. Chem tech, 1993, 30-33.
[6] Zana R. Dimeric and oligomeric surfactants. Behavior at interfaces and in aqueous solution: a review[J]. Advances in colloid and interface science,2002,97,205-253.
[7] Bunton C. A.,Robinson J.,Schaak J.,et al.Catalysis of nucleophilic substitutions by micelles of dicationic detergents[J].Org.Chem,1971,36(16):2346-2350.
[8] Zhu Y.P.,Masuyama A.,Kobata Y. Preparation and Surface Active Properties of Amphipathic Compounds with Two Sulfate groups and Two Lipophilic Alkyl chains[J]. J. Am. Oil Chem. Soc,1990,67(7):459-463.
[9] Menger F.M.,Littau C.A. Gemini surfactants-a new class of self-assembling molecules[J]. J.Am.Chem.Soc,1993,115(22):10083-10090.
[10] Menger F.M.,Littan C.A. Gemini surfactants: synthesis and properties[J].J.Am.Chem. Soc,1991(113):1451-1452.
[11] Alami E, Beinert G, Zana R, et al. Alkanediyl-.alpha,omega. -bis(dimethylalkyl ammoniumbromide) surfactants. 3.Behavior at the air water interface[J]. Langmuir,1993,9, 1465-1467.
[12] Alami E., Levy H., Zana R., Skoulios A. Alkanediyl-.alpha.,.omega.-bis(dimethylalkyl ammonium bromide) surfactants. 2. Structure of the lyotropic mesophases in the presence of water[J]. Langmuir,1993,9,940-944.
[13]赵剑曦.新一代表面活性剂:Gemini[J].化学进展,1999,11(4):348-357.
[14]袁淑军,吕春绪,蔡春.一种席夫碱型表面活性剂的合成及其表面活性[J].精细化工, 2002,19(11):626-628.
[15]黄智,李成海,梁宇宁等.N,N’一双月桂酞基乙二胺二乙酸钠合成方法的改进[J].精细化工,2002,19(11):621-622.
[16]朱森,程发,郑宝江.Gemini阴离子表面活性剂水溶液的界面活性[J].应用化学,2005,22 (7):792-795.
[17]赵田红,胡星琪,赵法军.一种阴离子型双子表面活性剂的合成与表征[J].日用化学工业,2007,37(5):293-297.
[18] Xigang Dua,Yao Lua,, Ling Li Jinben Wang, Zhengyu Yang. Synthesis and unusual properties of novel alkylbenzene sulfonate gemini surfactants[J]. Colloids and Surfaces A: Physicochem. Eng.Aspects, 2006,290:132–137.
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