邻苯二甲酸酯Gemini表面活性剂的合成及性能

采用N,N-二甲基乙醇胺与邻苯二甲酰氯反应得到二(二甲基胺基乙基)邻苯二甲酸酯(Ⅰ),然后Ⅰ再与正溴代十六烷反应,经处理后得到邻苯二甲酸酯基Gemini表面活性剂SHZ16,收率83%(以邻苯二甲酰氯计)。用两相滴定法分析其质量分数为99.2%。采用电导法测定了其CMC值为2.02×10-5mol/L,采用滴体积法测定了γCMC为41.87 mN/m,并考察了其增溶性、黏度、乳化性能和泡沫性质,该性能优于传统表面活性剂十二烷基硫酸钠(SDS)。     

表面活性剂用於硝基二苯醚的相转移催化合成

2-硝基二苯醚和4-硝基二苯醚是重要的有机合成中间体,广泛用于染料、除草剂、杀菌剂等精细化工产品的制造。本文选择一定的阳离子表面活性剂及聚醚,通过相转移催化反应合成了上述中间体。讨论了不同的阳离子表面活性剂和聚乙二醇及其开链醚对反应的影响。     

以壬基酚为基非离子双子表面活性剂的合成及其表面性能

以壬基酚和甲醛的二聚体为原料,合成了一种新型结构的非离子双子表面活性剂,总收率为20%。利用IR、1HNMR表征产物结构,证明了所得产物为目标产物。并利用Wilhelmy-Plate法测定了水溶液中这种非离子双子表面活性剂的CMC和表面张力:CMC=0.0034 mmol/L,与相应结构的单子表面活性剂相比(CMC=0.1995 mmol/L),CMC提高了2个数量级;表面张力为35.18 mN/m。     

对-烷基-苄基聚氧乙烯醚羧酸甜菜碱的合成与表面活性

以脂肪酸、苯、二缩三乙二醇为原料,经酰化反应、黄鸣龙还原反应、氯甲基化反应、威廉逊成醚反应、卤化反应、季铵化反应,合成出了3个对烷基苄基聚氧乙烯醚羧酸甜菜碱两性离子表面活性剂。用IR、1HNMR和ESI-MS对产物进行了结构鉴定。用Wilhelmy-plate法测定了30℃时它们在水溶液中的临界胶束浓度(CMC)和临界胶束浓度下的表面张力(γCMC)。实验表明,纯水溶液中表面活性剂的临界胶束浓度(CMC)为10-4～10-6mol/L,临界胶束浓度下的表面张力(γCMC)为27～30 mN/m;随着苯环上长链烷基碳数(n=8、10、12)的增加,CMC分别为1.12×10-4、1.51×10-5、6.21×10-6 mol/L;γCMC分别为27.9、28.4、29.9 mN/m。结果表明,该类表面活性剂具有比较好的表面活性。     

双十二酰胺基磺酸盐型阴离子表面活性剂的合成及性能

以十二酸,二乙烯三胺为原料,氢氧化钾为催化剂,经酰胺化反应合成了中间体N,N-双-(十二酰基乙基)胺,再在甲苯/丙酮混合溶剂回流的条件下,与过量的丙烷磺内酯反应,经中和后制得双十二酰胺基磺酸钠阴离子表面活性剂。用红外光谱、质谱以及核磁共振氢谱对中间体及目标产物的结构进行了表征。使用电导率法测定双十二酰胺基磺酸钠的Krafft点为37.3℃,因此,在45℃下使用悬滴法测其表面张力。根据γ-lgc曲线得到其临界胶束浓度CMC为6.40×10-4mol/L,最低表面张力γCMC为37.33 mN/m。在45℃下使用旋转液滴法测定了不同浓度的双十二酰胺基磺酸钠水溶液与壬烷的界面张力。NaCl的质量分数在0~5%,双十二酰胺基磺酸钠的浓度为1×10-4mol/L,当NaCl的质量分数为5%时,壬烷与水的界面张力最低达3.39×10-3mN/m,且不会发生盐析现象。     

长链烷基苯磺酸钠Gemini表面活性剂的合成和表面活性

以脂肪酸、苯酚、乙二醇为原料,经酰化反应、酯化反应、Fries重排、氢化还原反应、磺化以及中和反应等步骤,合成出3种长链烷基苯磺酸钠Gem in i表面活性剂。用IR、1HNMR和ESI-MS对产物进行了结构鉴定。以W ilhelmy-p late法测定了30℃时它们在水溶液中的临界胶束浓度(CMC)和临界胶束浓度下的表面张力(γCMC)。纯水溶液中其临界胶束浓度(CMC)为10-4~10-5mol/L,γCMC为35~37 mN/m;随着苯环上长链烷基碳数(n=8、10、12)的增加,CMC分别为5.94×10-4、1.53×10-5、0.46×10-5mol/L;γCMC分别为36.9、34.4、34.4 mN/m。结果表明,此类表面活性剂具有比较好的表面活性。     

不同类型的离子表面活性剂对甲苯的增溶作用

通过电导法测定SDBS、CTAB、FMES 3种离子表面活性剂水溶液在25,30,35℃时的临界胶束浓度(CMC),并依据CMC和范特霍夫方程计算了3种体系下的ΔH■、ΔS■和ΔG■,测定无机盐(NaCl、Na_2SO_4)和有机物(乙醇、十二醇)对表面活性剂增溶甲苯的影响。结果表明,3种体系下ΔG■均为负,这说明3种表面活性剂在水溶液中均易于形成胶团;3种离子表面活性剂的CMC大小顺序与对甲苯溶解量的大小顺序不同,说明CMC大小并不是影响甲苯增溶的唯一因素;添加一定量有机物[n(乙醇)∶n(FMES)=1∶4]或者无机盐(0.2 mol/L浓度的NaCl)对甲苯增溶效果更好。     

不同类型的离子表面活性剂对甲苯的增溶作用

通过电导法测定SDBS、CTAB、FMES 3种离子表面活性剂水溶液在25,30,35℃时的临界胶束浓度(CMC),并依据CMC和范特霍夫方程计算了3种体系下的ΔH■、ΔS■和ΔG■,测定无机盐(NaCl、Na_2SO_4)和有机物(乙醇、十二醇)对表面活性剂增溶甲苯的影响。结果表明,3种体系下ΔG■均为负,这说明3种表面活性剂在水溶液中均易于形成胶团;3种离子表面活性剂的CMC大小顺序与对甲苯溶解量的大小顺序不同,说明CMC大小并不是影响甲苯增溶的唯一因素;添加一定量有机物[n(乙醇)∶n(FMES)=1∶4]或者无机盐(0.2 mol/L浓度的NaCl)对甲苯增溶效果更好。     

烷基二苯醚二磺酸盐的制备与性能表征

制备了一类由刚性基团联接的特殊双亲水基型阴离子表面活性剂———十二烷基二苯醚二磺酸钠(C12-MADS)、双十二烷基二苯醚二磺酸钠(C12-DADS)及十六烷基二苯醚二磺酸钠(C16-MADS),并对其性能进行了研究。25℃时3种烷基二苯醚二磺酸钠的CMC分别为1 16×10-3、1 10×10-5和4 51×10-4mol/L,γCMC分别为44 9、43 5和46 8mN/m,C12-MADS和C16-MADS在浓度分别为2 21×10-2和3 80×10-2mol/L时的胶束聚集数(Nm)分别为24和29。合成的烷基二苯醚二磺酸钠在质量分数高达0 1的无机酸、碱和盐溶液中保持稳定,发泡性低于烷基苯磺酸钠(LAS),但乳化性能优于LAS。C12-MADS在650mg/L硬水中去污比值为14 05%,明显高于LAS(7 18%)。C12-MADS和C12-DADS在4d后的生物降解度≥90%。该类表面活性剂具有优良的应用性能。     

一种双偶氮有色表面活性剂的合成及性能

通过偶合反应合成了4个不同碳链长度的3′-脂肪酰胺基-4′-羟基偶氮苯-2-(4-磺基苯偶氮基)-4-磺酸(BAS),这些化合物同时有表面活性剂和双偶氮染料的结构,其中,脂肪酰胺基为10(C10),12(C12)和14(C14)个碳的产物有较好的表面活性,是有色的表面活性剂。表面活性最好的C14 BAS的γCMC为52.7 mN/m,最低表面张力为50.2 mN/m。虽然BAS的上染率较低(7%~11%),染后的布块颜色较浅,但染色布吸附食用油后,用水洗脱的油量明显比白布多,是其2~3倍。     

温度及无机盐对LMEE和SDS混合溶液表面张力的影响

通过表面张力的测定,研究了温度和不同无机盐对月桂酸甲酯乙氧基化物(laurylmethylesterethoxylate,简称LMEE)与十二烷基硫酸钠(SDS)复配物表面张力及临界胶束浓度(CMC)的影响。研究表明:混合体系的CMC在很宽的复配比例内出现最低值,25℃、未加无机盐时可使CMC最低降至3 8×10-5mol/L;温度对复配体系表面张力的影响较小,温度上升复配物的CMC略有降低。3种价态无机盐的加入均可使复配物的CMC有所降低,但与单一表面活性剂相比,温度和无机盐对复配物的CMC影响均不大,说明复配体系的抗温变及抗盐能力均有增强。     

Properties of aqueous solution of sodium cyclododecyl sulfate

Sodium cyclododecyl sulfate was prepared from cyclododecyl alcohol and chlorosulfonic acid to investigate the physical and surface active properties of the surfactant. Its Krafft point, critical micelle concentration (CMC), surface tension, emulsifying power, wetting time and dispersing power were examined and compared with those of sodium dodecyl sulfate which has a linear structure and contains the same number of carbon atoms in the hydrophobic portion. The sodium cyclododecyl sulfate, in contrast to the sodium dodecyl sulfate, had a higher (about two times) Krafft point, much larger (about 10 times) CMC, showed the same excellent wetting property, but exhibited lower emulsifying power. Also the sodium cyclododecyl sulfate is more insoluble (as shown by the Krafft point) than the sodium dodecyl sulfate, while calcium ion stability of the cyclododecyl sulfate surfactant is greater than that of the linear anionic surfactant.     

Surface activity of mixtures of dodecyl trimethyl ammonium bromide with sodium perfluorooctanoate and sodium octanoate

In this study, the surface tension of mixtures of cationic surfactant dodecyl trimethylammonium bromide (DTAB) and anionic surfactant sodium perfluorooctanoate (SPFO) was evaluated as a function of DTAB-SPFO composition and total surfactant concentration, with and without added electrolyte. It was found that the critical micelle concentration (CMC) of these mixtures was reduced by more than two orders of magnitude when compared to the CMC of SPFO and DTAB alone. The surface tension, after CMC, of the mixtures was close to that of SPFO with added electrolyte and even lower than that of SPFO without added electrolyte. Using the appropriate, combination of SPFO and DTAB, surface tensions near 18 mJ/m² were obtained using a concentration 1/500 of that required for SPFO alone. When these results were compared to those obtained for DTAB-sodium octanoate (SOCT) mixtures, it was evident that the DTAB-SPFO system shows a larger degree of synergism than the DTAB-SOCT system. Contact angle measurements on Teflon^® surfaces corroborates that the lower surface tension of DTAB-SPFO mixtures improves wetting on these hydrophobic surfaces. Using the regular solution theory to interpret the data of CMC and C45mJ/m² (monolayer formation) versus DTAB-SPFO composition, it was concluded that even when small concentrations of SPFO are introduced in the mixture, the composition of the micelles (at the CMC) and monolayer adsorbed at the air-water interface tends to be equimolar in SPFO and DTAB.     

Synthesis and Micellization Properties of New Anionic Reactive Surfactants Based on Hydrogenated Cardanol

We report the synthesis, characterization and micellization properties of two anionic reactive surfactants based on 3-pentadecyl phenol obtainable from a renewable resource, cardanol. The synthesis is achieved through simple chemical transformations, first converting the phenol to the acrylate that is sulfonated in a second step. The products were characterized by elemental analysis and spectroscopic techniques. The surfactant properties of the sulfonated acrylates were measured and compared with the standard non-reactive anionic surfactant sodium dodecyl sulfonate. The micellization behavior of aqueous solutions was studied using conductivity, surface tension measurements, and the fluorescence probe technique based on diphenyl hexatriene. Characterization by surface tension measurements facilitated the determination of basic surfactant properties like the critical micelle concentration (CMC), the surface tension at the CMC, surface excess and area per surfactant molecule. The Gibbs free energy of micellization showed a negative value suggesting spontaneous micellization in aqueous solution. The micellization of the surfmer with an ethylene spacer between the phenyl ring and the acrylate group seems to be enhanced as indicated by the lower surface excess and lower free energy. Its CMC was also lower.     

一种含氟烷基磷酸酯类氟碳表面活性剂的复配研究

研究了含氟烷基磷酸单酯类表面活性剂[分子式为H(CF2)6CH2OPO(ONa)2,记为DFH-PS]与无机盐和普通碳氢表面活性剂的复配性能,研究结果表明,DFH-PS水溶液最低表面张力为23.73 mN/m;当NaCl浓度为0.2 mol/L时,可使DFH-PS水溶液最低表面张力下降到21.62 mN/m;阴离子碳氢表面活性剂十二烷基硫酸钠(SDS)对该含氟表面活性剂影响显著,当n(DFH-PS)∶n(SDS)=5∶1时,可使水溶液表面张力在很低浓度时降至22.22 mN/m;与非离子表面活性剂辛基酚聚氧乙烯(10)醚(OP-10)混合,当n(DFH-PS)∶n(OP-10)=8∶1时,可使水溶液表面张力降至27.0 mN/m。     

The Adsorption Layer in the System: Carboxymethylcellulose/Surfactants/NaCl/MnO2

The influence of surfactants (anionic sodium dodecyl sulfate, and nonionic tert-octylphenol ethoxylate with 9.5EO) and their mixtures on the adsorption of carboxymethylcellulose (CMC) in the presence of 0.001?M NaCl on the manganese dioxide surface (MnO(2)) was studied. The increase in CMC adsorption was observed in all measured systems in the presence of surfactants. The reason for this is the formation of complexes between polymer macromolecules and surfactants. Moreover, the dependence between the amount of surfactants adsorption and the CMC initial concentration was also studied. It proves that surfactant adsorption does not depend on the initial concentration of CMC. Another observation is that the increase in pH caused the decrease in CMC adsorption. The explanation of this phenomenon is connected with the influence of pH on the dissociation degree of the polyelectrolyte, kind and concentration of?the surface active groups of the adsorbent. To characterize the compact and diffuse adsorption layer the surface charge density and the zeta potential of MnO(2) in the presence of CMC and surfactants were measured. The surface charge density of MnO(2) decreases in the presence of CMC or CMC/surfactant complexes. This is due to the presence of negatively charged groups in the compact part of the electric double layer. The zeta potential of MnO(2) is also lower in the presence of CMC and the CMC/surfactants complexes. The main reason for that is the shift of the slipping plane towards the bulk solution.     

R_(12)TAC-SDS混合溶液的表面张力和泡沫性能

测定了 3 十二烷氧基 2 羟丙基三甲基氯化铵 (R12 TAC)和十二烷基硫酸钠 (SDS)复配体系的表面张力和泡沫性能。实验表明 ,复配体系的CMC及γCMC均低于单一组分。当R12 TAC和SDS以等量比复配时 ,体系表现出良好的泡沫性能。其中起泡性参数Cs为 1.99mmol/L ,Rmv 为0 86 ,稳泡性参数Ct为 2 .5 0mmol/L ,t1/ 2 m 为 91.5s。对相互作用参数的计算表明 ,该复配体系具有强烈的增效作用     

Synthesis of Thumba,Castor and Sal Fatty Ethanolamide-Based Anionic Surfactants

The study involved the preparation and evaluation of anionic surfactants from non-edible oil based thumba (containing unsaturated-rich fatty acids, 80.9 %), castor (containing ricinoleic acid, a hydroxy fatty acid 89.3 %) and sal (containing saturated-rich fatty acids, 56.5 %). The oils extracted from these seeds (using Soxhlet) were reacted with monoethanolamine and diethanolamine to get corresponding fatty mono- and diethanolamides. The ethanolamides were sulfated using chlorosulfonic acid and the sulfated sodium salts were evaluated for surfactant properties namely surface tension, critical micelle concentration (CMC), emulsifying property, wetting, foaming power and calcium tolerance. The properties were compared with sodium dodecyl sulfate (SDS) a well known anionic surfactant. Among the different sulfated sodium salts of ethanolamides, thumba showed superior surfactant properties compared to castor and sal. Sulfated sodium salt of thumba monoethanolamide showed better properties (CMC, 0.035 mmol/L, surface tension 30.2 mN/m and calcium tolerance >1,000 ml, 0.5 % calcium acetate solution) compared to sulfated sodium salts of thumba diethanolamides, followed by sulfated sodium salts of castor monoethanolamide (CMC 0.037 mmol/L, surface tension 35.3 mN/m and calcium tolerance >1,000 ml, 0.5 % calcium acetate solution). Sal being saturated rich was not properly soluble in water and showed poor surfactant properties compared to the other two. Also the sulfated sodium salts of thumba and castor ethanolamides exhibited superior properties compared to SDS.     

Physicochemical Properties of Novel Phosphobetaine Zwitterionic Surfactants and Mixed Systems with an Anionic Surfactant

A series of novel zwitterionic phosphobetaine (PPBT) surfactants were synthesized using long chain fatty alcohol, epichlorohydrin, dimethylamine and sodium dihydrogen phosphate as raw materials. The physicochemical properties of the phosphobetaine surfactants such as isoelectric point, foaming, surface tension, critical micelle concentration (CMC) and Krafft point were measured. Low CMC and surface tension values indicated the surface activities of the phosphobetaine surfactants were quite excellent. The CMC and surface tension values of PPBT/SDS mixed systems were determined. It was found both of CMC and surface tension values decreased compared with single surfactant system because of the association between dodecyl sulfate anions and cationic groups in phosphobetaine by electrostatic attraction.     

Guerbet十四醇聚氧乙烯醚硫酸钠的合成与表面活性

以Guerbet十四醇 (C14 GA)为中间体 ,经Williamson反应合成Guerbet十四醇聚氧乙烯醚醇〔C14 GA(EO) nH ,n =1,2 ,4〕 ,再经氯磺酸酯化及NaOH中和 ,得到阴离子表面活性剂Guerbet十四醇聚氧乙烯醚硫酸钠〔C14 GA(EO) nS ,n =1,2 ,4〕。用IR、NMR和元素分析测定了所合成的表面活性剂的结构 ,并利用表面张力法测定了这些表面活性剂水溶液的表面活性。实验结果表明 :所合成的表面活性剂的结构分别为C14 GAEOS (A) ,C14 GA(EO) 2 S(B)和C14 GA(EO) 4 S(C) ;这些表面活性剂其临界胶束浓度CMC(mmol/L) ,在CMC时的表面张力γCMC(mN/m)和Krafft点 (℃ )分别为A :2 5 8mmol/L ,2 7 6mN/m ,5 9℃ ;B :0 80mmol/L ,2 6 4mN/m ,2℃和C :0 12mmol/L ,2 5 3mN/m ,0℃。均比常用的直链阴离子表面活性剂C12 H2 5SO4Na(8.6mmol/L ,4 1 2mN/m ,16℃ )有更低的CMC ,γCMC和Krafft点 ;聚氧乙烯基的引入 ,对降低CMC ,γCMC和Krafft点的效果随氧乙烯基团数目的增多 (由 1增至 4 )而加大。讨论了表面活性剂的结构和表面活性的关系