阴离子Gemini表面活性剂的合成进展

Gemini表面活性剂,这种新颖表面活性剂的研究已成为当前表面化学领域的热点课题,它是通过联接基团将2个单链单头基表面活性剂在离子头基处以化学键方式联接起来。阴离子Gemini表面活性剂就是其中一种,按照其结构特点,可分为磺酸型、羧酸型、磷酸型等。作者综述了阴离子Gemini表面活性剂的研究进展和合成现状。     

Kinetics of precipitation of surfactants. I. Anionic surfactants with calcium and with cationic surfactants

Isoperibol calorimetry was used to measure the rates of precipitation for aqueous solutions of several anionic surfactants with calcium and of anionic and cationic surfactants. A monomer concentration-dependent supersaturation ratio was used to describe the relative rates of precipitation for the surfactant systems studied. This supersaturation ratio allows for the relative rates of precipitation of any surfactant solution to be compared whether micelles are present in solution or not. In general, as the supersaturation ratio increases, the rate of precipitation decreases and the induction time decreases, bot above and below the critical micelle concentration (CMC). The rate of precipitation of sodium dodecyl sulfate (SDS) with dodecyl pyridinium chloride is much slower than the rate of precipitation of the anionic surfactants with calcium for similar supersaturation ratios. The rate of precipitation of SDS with calcium is slightly faster than the rate of precipitation of sodium octyl benzene sulfonate for similar supersaturation ratios. Studies of precipitate crystals, conducted using image analysis, showed that size and shape dependent on the initial supersaturation, the precipitating surfactant molecule, and the extent of aging (until an equilibrium size and shape was reached). Also, differences in the appearance of crystals formed from solutions above and below the CMC were observed. These were most likely due to the difference in supersaturation of these solutions. The crystals formed due to precipitation of SDS with calcium at a concentration above the CMC formed flat trapezoidal, rhombic and hexagonal shapes. These aged into clusters by 1 wk. For a solution that was precipitated at concentrations beginning below the CMC, the crystals began as elongated and rhombic flat plates and aged into trapezoidal, rhombic, and needle-like structures.     

Mixtures of anionic and cationic surfactants with single and twin head groups: Adsorption and precipitation studies

This research reports on the adsorption and precipitation of mixtures of anionic and cationic surfactants having single and twin head groups. The surfactant mixtures investigated were: (i) a single-head anionic surfactant, sodium dodecyl sulfate (SDS), in a mixture with the twin-head cationic surfactant pentamethyl-octadecyl-1,3-propane diammonium dichloride (PODD)—adsorption was studied on negatively charged silica; and (ii) a twin-head anionic surfactant, sodium hexadecyl-diphenyloxide disulfonate (SHDPDS), and the single-head cationic surfactant dodecylpyridinium chloride (DPCI)—adsorption was studied on positively charged alumina. Whereas the mixed surfactant system of SHDPDS/DPCI showed adsorption on alumina that was comparable to the of SHDPDS alone, the mixed surfactant system of SDS/PODD showed increased adsorption on silica as compared with PODD alone. The adsorption of the SDS/PODD mixture increased as the anionic and cationic system approached an equimolar ratio. Precipitation diagrams for mixtures of single- and twin-head surfactant systems showed smaller precipitation areas than for single-head-only surfactant mixtures. Thus, the combination of single- and double-head surfactants helps reduce the precipitation region and can increase the adsorption levels, although the magnitude of the effect is a function of the specific surfactants used.     

阴离子-阳离子-非离子三元复配型表面活性剂制备微乳化柴油

以磁力搅拌器为分散手段,油酸、十二烷基三甲基溴化铵(DTAB)或十四烷基三甲基溴化铵(TTAB)为主表面活性剂,在NH3.H2O存在的情况下,使用各种醇作助剂制备微乳化柴油,并对其增溶水量的各种影响因素进行研究。结果表明:复配体系TTAB/油酸/NH3.H2O比DTAB/油酸/NH3.H2O的增溶效果好,且在TTAB、油酸、NH3.H2O的摩尔比为1∶20∶17,复配乳化剂用量为3 g,正丁醇用量为3 mL,以0.15 mol/L的NaBr水溶液代替水相制备的微乳化柴油增溶水量最大、成本最低。所制备的微乳化柴油粒径在50～60 nm之间,稳定时间在190 d以上,黏度、密度、腐蚀性均符合国家标准。     

Study on the influence of anionic and cationic surfactant on Au-colloid modified electrode function by cyclic voltammetry and electrochemical impedance techniques

The influence of different surfactants on Au-colloid modified electrode function has been investigated by using cyclic voltammetry and electrochemical impedance techniques. Colloidal Au was self-assembled onto the gold electrode through the thiol-groups of 1,6-hexanedithiol (HDT) monolayer. It was found that some HDT molecules stood on the gold electrode and some molecules lay on the electrode by using the quartz crystal microbalance (QCM). A cathodic peak at about 0.486 V (vs. SCE) was observed at the bare gold electrode and the Au-colloid modified electrode. Cyclic voltammetry was used to investigate the influence of different surfactants on the cathodic peak of Au-colloid modified electrode. Electrochemical impedance technique was also used to study the electron transfer ability of the redox probe on Au-colloid modified electrode after being immersed in different surfactants. The results showed that anionic surfactant and cationic surfactant exhibit different behaviors, the reason of which was discussed.     

Electrochemical properties of supercapacitors operating in aqueous electrolyte with surfactants

Effect of surfactants present in alkaline and acidic solutions on the capacitance of carbon electrodes has been studied. Three various types of surfactants, i.e. sodium dodecyl sulphate (SDS), tetrapropylammonium bromide (TPAB) and non-ionic such as polymer of polyethylene glycol and p-t-octylophenol (Triton X-100) have been selected for this target. Concentration of these electrolyte additives was 0.005 mol L⁻¹. Decreasing the surface tension in the electrode/electrolyte interface allows better penetration of electrolyte into the pores. However, surfactants played a different role depending on the electrode polarity. Detailed analysis of capacitance versus current load, frequency dependence as well as self-discharge and cyclability proved especially a profitable effect of Triton X-100 on capacitor operating in alkaline solution.     

Mixtures of anionic and cationic surfactants with single and twin head groups: Solubilization and adsolubilization of styrene and ethylcyclohexane

Mixtures of anionic and cationic surfactants with single and twin head groups were used to solubilized styrene and ethylcyclohexane into mixed micelles and adsolubilize them into mixed admicelles on silica and alumina surfaces. Two combinations of anionic and cationic surfactants were studied: (i) a single-head anionic surfactant, sodium dodecyl sulfate (SDS), with a twin-head cationic surfactant, pentamethyl-octadecyl-1,3-propane diammonium dichloride (PODD), and (ii) a twin-head anionic surfactant, sodium hexadecyl-diphenyloxide disulfonate (SHDPDS), with a single-head cationic surfactant, dodecylpyridinium chloride (DPCl). Mixtures of SDS/PODD showed solubilization synergism (increased oil solubilization capacity) when mixed at a molar ratio of 1∶3; however, the SHD-PDS/DPCl mixture at a ratio of 3∶1 did not show solubilization enhancement over SHDPDS alone. Adsolubilization studies of SDS/PODD (enriched in PODD) adsorbed on negatively charged silica and SHDPDS/DPCl adsorbed on positively charged alumina showed that while mixtures of anionic and cationic surfactants had little effect on the adsolubilization of styrene, the adsolubilization of ethylcyclohexane was greater in mixed SHPDS/DPCl systems than for SHDPDS alone. Finally, it was concluded that whereas mixing anionic and cationic surfactants with single and double head groups can improve the solubilization capacity of micelles or admicelles, the magnitude of the solubilization enhancement depends on the molecular structure of the surfactant and the ratio of anionic surfactant to cationic surfactant in the micelle or admicelle.     

Mechanism of the enhanced spreading of some mixtures of anionic and cationic hydrocarbon chain surfactants on a highly hydrophobic polyethylene surface

The objective of this investigation was to measure the interfacial properties and interactions among mixtures of different cationic and anionic surfactants at the hydrophobic solid/aqueous solution interface to explain the different spreading factors or behavior of the mixed surfactants on a highly hydrophobic polyethylene (PE) film. A synergistic effect in the spreading of the mixed surfactant solutions on the PE film was observed when the surfactants were added sequentially. Other interfacial phenomena related to this surfactant spreading, such as interaction parameters at the solid/liquid (S/L) and liquid/air (L/A) interfaces in the mixtures adsorbed at various interfaces and dynamic contact angles of the mixed surfactant solutions during the process of spreading on the PE substrate, were investigated to obtain insight into this enhanced spreading. All the interaction parameters were more negative than −20, indicating very strong interaction between these cationic and anionic surfactants. The interaction parameters at the S/L interface were more negative than at the L/A interface, showing that the attractive interaction at the S/L interface was stronger than at the L/A interface. The spreading was related to the difference in the interaction parameters at the S/L and L/A interfaces and to the dynamic contact angle.     

Surface and aqueous properties of anionic gemini surfactants having dialkyl amide,carboxyl, and carboxylate groups

A systematic study of the equilibrium surface properties (in water and in the presence of 10⁻² M NaCl) of a novel series of anionic gemini surfactants, (CH₂)₂[N(COC_nH_2n+1)CH(COOH)CH₂COOH]·2NaOH (GA), where (n+1)=8, 10, 12, 14, and 16, was investigated. The responses of humans to closed patch tests with (CH₂)₂[N(COC₁₁H₂₃)CH(COOH)−CH₂COOH]₂·2NaOH (GA-12) were also investigated. Premicellar self-aggregation (both in water and 10⁻² M NaCl) occurred when the N-acyl group contained more than 14 carbon atoms, since the critical micelle concentration (CMC) values decreased and the pC₂₀ values increased as (n+1) increased for (n+1) ≤14; the CMC values increased and the pC ₂₀ values decreased as (n+1) increased for (n+1)>14, both in water and in 10⁻² M NaCl. The absence of a break in the specific conductance-surfactant molar concentration plots for the GA homologs indicates protonation of the carboxylate group and strong Na⁺ release during micellization. This is a structural characteristic of the anionic geminis having N-dialkylamide and carboxylate groups in a molecule. The skin irritation potential of GA-12 is lower than that of the corresponding “monomer”, C₁₁H₂₃CON(CH₃)CH(COOH)CH₂(COOH)·NaOH, and the analog, C₁₁H₂₃CON(CH₃)CH₂COONa·H₂O.     

含酰胺基双子阳离子表面活性剂的合成与性能研究

以N,N-二甲基丙二胺分别与十二酸、十四酸、十六酸和十八酸反应得到酰胺基叔胺,再制成其盐酸盐,盐酸盐与环氧氯丙烷在水溶剂中合成了相应的含酰胺基双子(gemini)阳离子表面活性剂,采用红外光谱、质谱、元素分析、核磁共振波谱进行了结构表征,并测定了阳离子表面活性剂表面化学性能.结果表明,真空干燥后含酰胺基gemini阳离子表面活性剂的质量分数大于98%,该含酰胺基gemini阳离子表面活性剂具有很强的表面吸附和胶束生成能力,随着脂肪碳链长度由12增加到18,cmc由9.12×10-5mol·L-1减少至3.31×10-5mol·L-1,ccmc/c20由3.02增加到3.98,Krafft点也有升高的趋势.     

Effect of hydrophilic group on thin film formation using redox-active surfactants with an azobenzene group

Thin films of organic pigments were prepared at higher than pH 1 by the contact plating method using an anionic surfactant (AZNa, first figure of this article (part c) (n = 4)) containing an azobenzene moiety. The effects of hydrophilic group of the surfactants on the rate of following reaction of the reduction product were studied by cyclic voltammetry. The positive shift of the reduction peak potential of AZNa compared to those of cationic and non-ionic surfactants was ascribed to higher rate of following reaction of reduction product due to the presence of the anionic hydrophilic group of the surfactant. The present investigation revealed that the anionic hydrophilic group accelerates the cleavage of the NN bond of the azobenzene group. This phenomenon enabled us to prepare the organic thin film at higher pH condition.     

生物可降解型阳离子酯类表面活性剂的研究

以自制的失水甘油基三甲基氯化铵(GTMAC)和硬脂酸为原料,经一步反应合成阳离子单酯表面活性剂(CMESA)。研究了反应介质、反应温度和反应时间对生成物CMESA收率的影响,通过元素分析、官能团分析和红外光谱确证其化学结构,较佳反应条件为:n(GTMAC)∶n(硬脂酸)=1∶1,异丙醇为溶剂,85℃,反应16h,CMESA收率86 8%。接着采用电导法测临界胶团浓度(cmc),拉环法测表面张力(γ),得到20℃下CMESAcmc为0 035mmol/L,在cmc时的γ=44 95mN·m-1。最后研究了在静态时厌氧污泥对CMESA的作用,结果表明:厌氧污泥对CMESA适应性强,其产甲烷气的量不受影响,IC50可能超过1 0g/L。     

离子选择电极法分析非离子／阴离子表面活性剂体系

利用自制表面活性剂离子选择电极,采用电位滴定法测定了非离子表面活性剂脂肪醇聚氧乙烯醚(AEO9)与阴离子表面活性剂十二烷基硫酸钠(SDS)混合溶液中的SDS浓度。当AEO9与SDS的摩尔比约小于2∶1时,可用此种方法定量测定混合体系中的SDS的浓度,与滴定单一SDS溶液的结果对照,相对误差在1%以内。     

Electrochemical degradation of anionic surfactants

This study was performed to investigate the electrochemical oxidation of anionic surfactants. In particular, a synthetic solution of sodium dodecyl benzene sulfonate and a real car wash wastewater were treated by galvanostatic electrolysis using a Ti–Ru–Sn ternary oxide and a boron-doped diamond (BDD) anode. Measurements of the Chemical Oxygen Demand (COD) and the concentration of the anionic surfactants were used to follow the oxidation. Using the Ti–Ru–Sn ternary oxide anode, the complete removal of COD and sodium dodecyl benzene sulfonate was obtained only in the presence of chloride ions that act as inorganic mediators. The oxidation rate was almost independent of current density and electrolyte flow rate. In the case of BDD the mineralisation of the sodium dodecyl benzene sulfonate was achieved in all experimental conditions due to reaction with hydroxyl radicals electrogenerated on the diamond surface during electrolysis. The COD removal rate increased with increase in electrolyte flow rate, indicating that the oxidation was mass-transfer controlled. Comparison of the results of the two electrodes showed that chlorine mediated oxidation at the Ti–Ru–Sn ternary oxide anode allowed a faster COD removal of both the synthetic solution and real car wash wastewater.     

阳离子型Gemini表面活性剂改性膨润土的制备及结构表征

以膨润土为原料,以系列阳离子Gemini表面活性剂(Gm-n-m)为插层剂制备了有机膨润土,利用红外光谱、X射线衍射及差热-热重分析对产物结构进行了表征,并探讨了温度、时间、搅拌速率及插层剂用量对有机膨润土结构的影响。结果表明,当Gm-n-m分子进入到膨润土层间后,其疏水性增强,层间距由1.51 nm增大到3.91 nm,有机物含量达到23.53%,且层间距明显大于单链CTAB改性膨润土的层间距。适宜的制备条件为:插层剂用量为钠基膨润土的40%,70℃下水浴反应3 h,搅拌速率为205 r/min。     

Adhesion of anionic surfactants to polymer surfaces and low-energy materials

To study the adhesion of the anionic surfactant sodium dodecyl sulfate (SDS) to various materials, a schematic molecular model of SDS was used which optimally correlates with its critical micelle concentration (c.m.c.) values under various conditions. Using the surface tension components and parameters of (a) the SDS apolar and polar moieties and (b) the polymeric surfaces of cellulose and nylon, the energy of adhesion of SDS to these polymeric surfaces as well as to a typical low-energy material (greasy dirt) in the guise of hexadecane was determined. It could be quantitatively shown (using a surface-thermodynamic approach) that SDS, in water, adheres more strongly to the low-energy (greasy dirt) compounds than to the polymeric materials. The c.m.c. of SDS was derived directly from the surface tension components and parameters of its apolar and polar moieties, and the ζ potential of its polar heads. The c.m.c. values obtained using this model correlate well with the published c.m.c. values obtained experimentally at different ionic strengths.     

Loading characteristics of filter pretreated with anionic surfactant for monodisperse solid particles

Anionic surfactant (sodium oleate, SO) was used to pretreat polypropylene fibrous filters to make them negatively charged. This work examines the effects on particle loading of an anionic surfactant-pretreated filter. Also, the effects of various factors, such as the particle size, the face velocity, concentration of the surfactant, and particle distribution (mono and poly) on the particle loading characteristics were evaluated.Experimental data reveal that the electric field of a filter treated with anionic surfactant (SO) could be directly measured using an electrofieldmeter, suggesting that the pretreatment with surfactant charged the filters. The results demonstrate that pretreating the filter with SO surfactant increases its particle-loading capacity. The clogging points of the untreated filter, and of the 0.01, 0.05 and 0.08 M SO-pretreated filter are 18, 23, 28 and 33 g/m². The loading behavior of the SO-pretreated filter depended on the size of the particles and the operating face velocity. Additionally, the loading behavior of the SO-pretreated filter with polydisperse particles is much the same as that with monodisperse particles. However, the clogging point of the SO-pretreated filter with polydisperse particles is higher than that with monodisperse equal size.     

表面活性剂在聚合物/蒙脱石纳米复合材料制备中的应用

简要叙述了蒙脱石的结构;综述了阳离子表面活性剂插层蒙脱石以形成有机蒙脱石的机理、插层方法以及阳离子表面活性剂的结构对被插层蒙脱石的层间距的影响;讨论了不同类型的聚合物/蒙脱石纳米复合材料制备方法;同时比较了所得到的纳米复合材料的力学性能、热性能与纯聚合物的力学性能和热性能。结果表明:前者的力学性能和热性能比后者均有较大程度的提高。最后提出了聚合物/蒙脱石纳米复合材料目前存在的问题、发展方向和应用前景等。     

阴离子双子表面活性剂合成现状及应用前景

在对传统单链表面活性剂进行分析的基础上,重点论述了阴离子双子表面活性剂的性质和实现产业化有可能采取的合成途径,并且介绍了目标阴离子双子表面活性剂的结构和表面活性,同时也对其在洗涤剂、化妆品和工业助剂等领域的应用前景进行了分析,最后也对其发展趋势进行了展望。     

Synthesis and properties of destructible anionic and cationic surfactants with a 1,3-dioxolane ring

A convenient synthetic method for the preparation of destructible surfactants containing a 1,3-dioxolane ring with various substituents is described. The substituents include carboxylate, quaternary ammonium, and several aliphatic alkyl groups, such as hydrophilic or hydrophobic groups. These novel surfactants had good surface activity, and were easily hydrolyzed under acidic conditions. They also catalyzed aliphatic halide substitution.