N-(α-苯氧基)十四酰牛磺酸钠的合成

以α-溴代十四酸乙酯、苯酚、牛磺酸为原料,经W illiam son醚化,水解,催化酰化等反应制备了一种芳氧基作疏水基团支链的牛磺酸盐类表面活性剂,即N-(α-苯氧基)十四酰牛磺酸钠(SPTT)。研究了W illiam son醚化制备α-苯氧基十四酸乙酯的反应条件,考察了几种常用酰化方法对于合成N-(α-苯氧基)十四酰牛磺酸钠的可行性。研究结果表明,醚化反应的最佳条件为:n(α-溴代十四酸乙酯)∶n(苯酚)∶n(K2CO3)=1.05∶11∶,DMF为溶剂,用苯回流分水3 h,α-苯氧基十四酸乙酯的收率为78.3%;合成N-(α-苯氧基)十四酰牛磺酸钠(SPTT)的最佳方法是催化酰化法,即在二环己基碳二亚胺(DCC)和N-羟基丁二酰亚胺(NHS)的催化下,α-苯氧基十四酸与牛磺酸及碳酸钠反应,n(α-苯氧基十四酸)∶n(DCC)∶n(NHS)∶n(牛磺酸)∶n(碳酸钠)=1∶1∶1∶1.5∶1.5,收率为72.3%。中间体及产物经FTIR,1HNMR,ESI-MS等表征,符合结构特征。     

氯化1-（三甲基硅甲基）-3-癸基咪唑的合成及性能

以咪唑、氢氧化钠和溴代癸烷为原料,经烷基化反应合成中间体N-癸基咪唑,再与氯甲基三甲基硅烷在微波条件下进行季铵化反应合成离子液体型表面活性剂——氯化1-(三甲基硅甲基)-3-癸基咪唑。通过IR、~1HNMR和~(13)CNMR对中间体和目标产物的结构进行了表征,测定了目标产物的热稳定性、表面活性及泡沫性能。结果表明,氯化1-(三甲基硅甲基)-3-癸基咪唑在297℃时基本分解完全,25℃时的临界胶束浓度(CMC)为4.12 mmol/L,临界胶束浓度时的表面张力(γCMC)为25.13 m N/m,表现出较高的表面活性。此外,该离子液体型表面活性剂的起泡力随表面活性剂浓度的升高而增强,但稳泡性较差。     

生物质腰果酚基Gemini表面活性剂的合成及性能研究

采用生物质原料腰果酚与1,4-二溴丁烷和氯磺酸反应合成了一种新型绿色腰果酚磺酸盐Gemini表面活性剂。并通过单因素实验对双醚反应进行条件优化,得到较优的反应条件:n(腰果酚)∶n(1,4-二溴丁烷)=2.10∶1,反应温度为150℃,反应时间为8 h,收率为85.16%。采用红外光谱和元素分析对双醚中间体和目标产物进行了结构表征。对合成的腰果酚磺酸盐Gemini表面活性剂进行了性能测定,并与传统的单基表面活性剂十二烷基苯磺酸钠进行了对比,其γcmc为35.06 m N/m,低于十二烷基苯磺酸钠(39.2 m N/m),CMC为0.05 mmol/L,比十二烷基苯磺酸钠(1.6 mmol/L)低2个数量级。同时,具有比十二烷基苯磺酸钠更好的起泡性和乳化性能,表现出良好的表面活性。     

一种非对称双尾阳离子表面活性剂的合成及表面活性研究

以N,N-二甲基丙二胺、1-溴-十四烷、辛酸等为原料,通过酰化和季铵化反应合成了3个非对称双尾阳离子表面活性剂,用IR和1HNMR表征了中间体和目标产物。酰胺化反应的最佳条件为:投料比n(正辛酸)∶n(N,N-二甲基丙二胺)=1∶1.1,反应温度为120℃,反应时间为10 h。目标产物的最低表面张力(γCMC)均在20～30mN/m,临界胶束浓度(CMC)均在10-5～10-6 mol/L,γCMC和CMC均远低于结构类似单尾表面活性剂的γCMC和CMC。双尾阳离子表面活性剂的泡沫半衰期(T1/2)为22～31 min,泡沫稳定性强于单尾表面活性剂。     

辛基-[ω-烷氧基-聚(氧乙烯)]基-苯磺酸钠的合成及表面活性

以正辛酸、苯酚、多缩乙二醇和溴代烷烃为原料,经酰化、酯化、Fries重排、催化加氢、威廉逊醚化及磺化等反应,合成了8种辛基-[ω-烷氧基-聚(氧乙烯)]基-苯磺酸钠表面活性剂。经红外、核磁和电喷雾质谱对产物进行了结构鉴定。用W ilhelmy法测定了该系列表面活性剂的表面张力。结果表明,合成的辛基-[ω-烷氧基-聚(氧乙烯)]基-苯磺酸钠结构明确,具有良好的表面活性,水溶液中CMC达到10-5mol/L数量级,γCMC最低达25.79mN/m;固定烷基碳数,随着EO数的增加,CMC和γCMC先降低后升高,当EO数为4时,增加烷基碳数,CMC显著降低,γCMC减小。     

新型喹啉Gemini表面活性剂的合成及界面吸附

以6-氨基喹啉，三光气，三乙胺为原料合成了对称的喹啉脲，通过其与三种溴代烷进行季铵化反应合成了喹啉双季铵盐，其结构经FT-IR，1H NMR，13CNMR和ESI-MS证实。对中间体喹啉脲及目标产物喹啉Gemini表面活性剂的合成条件进行了优化。合成中间体的反应条件为二氯甲烷做反应溶剂，n (6-氨基喹啉)∶n (三光气) = 5∶1，反应时间为6 h，收率可达88%。合成喹啉类Gemini表面活性剂的反应条件为DMF为反应溶剂，反应温度为110℃，n(中间体)∶n(溴代烷) = 1∶14，反应时间为8 h，收率可达74%。对目标产物喹啉Gemini表面活性剂在三氯甲烷-水体系中的界面张力进行了测定，结果表明：喹啉Gemini表面活性剂在三氯甲烷溶液内扩散到三氯甲烷-水界面是由纯扩散吸附控制的。     

一种新型吡啶Gemini表面活性剂的合成及表面活性

以3-氨基吡啶和固体光气为原料,一锅法合成中间体1,3-二(3-吡啶基)脲,然后再与溴代十二烷进行季铵化反应,生成了新型的吡啶阳离子Gemini表面活性剂。通过单因素试验法优化了反应条件,得到较佳工艺条件为:n(3-氨基吡啶)∶n(固体光气)=5∶1,二氯甲烷作反应溶剂,反应5h,得到产率为78%的中间体;n(中间体)∶n(溴代十二烷)=1∶10,110℃反应5 h,得到产率为90%的吡啶Gemini表面活性剂。通过FT-IR,~1H NMR,13C NMR和ESI-MS对所得产物的结构进行了表征,并对其表面活性进行了研究。结果表明,该Gemini表面活性剂的临界胶束浓度(cmc)为1.67×10~(-4)mol/L,γcmc为30.7 m N/m。     

新型喹啉类Gemini表面活性剂的合成及界面吸附

以6-氨基喹啉、三光气、三乙胺为原料合成了对称的喹啉脲,其与3种溴代烷进行季铵化反应合成了3种喹啉双季铵盐Gemini表面活性剂,其结构经FTIR、~1HNMR、~(13)CNMR和ESI-MS确证。对中间体喹啉脲及目标产物喹啉Gemini表面活性剂的合成条件进行了优化。合成中间体喹啉脲的最佳反应条件为:二氯甲烷为反应溶剂,n(6-氨基喹啉)∶n(三光气)=5∶1,反应时间为6 h,1,3-二-6-喹啉基脲的收率可达88%。合成喹啉类Gemini表面活性剂的最佳反应条件为:中间体喹啉脲(a)(3.2 g,10.2 mmol),DMF(15 mL)为溶剂,反应温度为110℃,n(1,3-二-6-喹啉基脲)∶n(溴代十二烷)=1∶14,反应时间为8 h,收率可达74%。对目标产物喹啉Gemini表面活性剂在三氯甲烷-水体系中的界面张力进行了测定,结果表明:喹啉Gemini表面活性剂在三氯甲烷溶液内扩散到三氯甲烷-水界面是由纯扩散吸附控制。     

m-n-m型Gemini季铵盐表面活性剂的合成及性能研究

以N,N-二甲基十四胺和1,8-二溴辛烷反应生成了14-8-14型Gemini季铵盐表面活性剂,通过单因素试验优化了反应条件,确定较佳合成条件为:N,N-二甲基胺的用量为5 mmol,N,N-二甲基胺与二溴烷烃的摩尔比为2.2:1,溶剂乙腈用量为10 mL,反应温度为80℃,反应时间为24 h,在此条件下合成了24种m-n-m型Gemini季铵盐表面活性剂,大部分反应的收率大于80%。采用吊环法对产物的表面张力进行了测定,分别研究了疏水烷基链、连接基对Gemini季铵盐表面活性剂表面活性的影响,研究发现,当连接基n相同时,随着疏水烷基链的增长(m10时),Gemini季铵盐表面活性剂的表面张力呈现先减小后增大的趋势,14-n-14型Gemini季铵盐表面活性剂呈现出最好的表面活性;当疏水烷基链m=14时,随着连接基n的增大,Gemini季铵盐表面活性剂的表面张力呈现先增大后减小的趋势。     

2-羟基-3-辛基-5-长链烷基苯磺酸钠的合成及表面活性

以脂肪酸、苯酚为原料,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,合成出了2-羟基-3-辛基-5-长链烷基苯磺酸钠表面活性剂。两相滴定法测定了产物的质量分数均大于99%;用核磁共振氢谱、傅立叶红外光谱和质谱对产物进行了结构鉴定。用悬挂滴法测定了30℃时该系列表面活性剂的表面张力。实验发现,纯水溶液中表面活性剂的临界胶束浓度(CMC)达到10-6mol/L数量级,临界胶束浓度下的表面张力(γCMC)均小于28 mN/m;随着苯环上长链烷基碳数(n=8,10,12)的增加,CMC降低,分别为1.06×10-5,3.35×10-6,2.65×10-6mol/L;而γCMC变化不明显,分别为26.77,26.89,27.22 mN/m。结果表明,此类表面活性剂具有比较好的表面活性。     

A New Anionic Oxalamide Lauryl Succinate Sodium Sulfonate Gemini Surfactant: Microwave-Assisted Synthesis and Surface Activities

An anionic Gemini surfactant, oxalamide lauryl succinate sodium sulfonate, was synthesized successfully through amidation, esterification and sulfonation reactions under microwave irradiation conditions by using maleic anhydride, ethylenediamine, lauryl alcohol, sodium sulfite as the starting materials. The best reaction conditions for synthesize the target product were obtained by single factor and orthogonal optimization methods. FTIR, elemental analysis and ¹H‐NMR analysis were used to confirm the chemical structure of the surfactant. The critical micelle concentration (CMC) in aqueous solution, surface tension, emulsification capacity and foaming power were determined. The critical micelle concentration and γ_CMC are respectively equal to 3.5 × 10^?4 mol L^?1 and 21.5 mN m^?1. It was found that microwave‐assisted synthesis is an efficient means of preparation of this anionic Gemini surfactant with shorter times and higher yields.     

邻苯二甲酸酯Gemini表面活性剂的合成及性能研究

研究采用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纯度为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CMC为41.87mN/m, 并研究了其増溶性、粘度、乳化性能和泡沫性质,其性能优于传统表面活性剂十二烷基硫酸钠（SDS）。     

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)。     

无机盐对磺酸盐型双子表面活性剂溶液表面性能的影响

在(30±0.2)℃下,用直接观察法、表面张力法和旋转液滴法考察了不同无机盐(NaCl、CaCl2和MgCl2)对磺酸盐型双子表面活性剂DJ溶液溶解性、临界胶束浓度(CMC)值和界面张力的影响。结果表明,磺酸盐型双子表面活性剂DJ具有良好的抗盐性,溶解度可以达到20 000 mg/L以上;在低盐度范围时(小于500 mg/L),随着无机盐质量浓度的增加,表面活性升高,CMC降低;随着阳离子(Na+、Ca2+和Mg2+)价数的增加,CMC降幅增大,且Ca2+的影响程度大于Mg2+;在无机盐质量浓度达到10 000 mg/L时,CMC呈上升趋势;无机盐的加入使溶液界面张力先降后升,然后趋于平稳。无机盐质量浓度在100～1 000 mg/L内,磺酸盐型双子表面活性剂DJ溶液的界面张力可以达到最低。     

Surface Activity and Performance Properties of Gemini Salts of Linear Alkylbenzene Sulfonate in Aqueous Solution

Gemini salts of linear alkylbenzene sulfonate (LABS) were prepared by neutralization of sulfonic acid with a series of low-molecular-weight diamines in aqueous solution. The equilibrium surface activity of Gemini salts of LABS was determined by measuring the surface tension as a function of surfactant concentration to determine the critical micelle concentration (CMC), surface tension at the CMC (γ_CMC), and the area per molecule at the air-water interface (Ų). Electrical conductivity was measured as a function of surfactant concentration to determine the CMC and counterion binding. Dynamic surface tension was measured using a bubble pressure tensiometer to infer the rate at which the surfactant migrates to the air-water interface. Equilibrium interfacial tension against mineral oil was measured using a spinning drop tensiometer. Dynamic interfacial tension was measured using a drop volume tensiometer. The surface tension, CMC, and interfacial tension of Gemini salts of LABS decreased compared to monovalent organic and inorganic salts. The CMC decreases with increasing molecular weight of the diamine spacer group. Dynamic surface and interfacial tension of Gemini salts of LABS are lower than monovalent salts. The foam volume of Gemini salts of LABS was determined using a high shear blender test. The foam volume of Gemini salts of LABS is lower than monovalent salts and depends on the size of the spacer group. Hard-surface cleaning was measured using artificial soil applied to white Formica tiles. Soil removal was determined by optical reflectance as a function of abrasion cycles. Gemini salts of LABS show reduced hard-surface cleaning performance compared to monovalent salts. Detergency of different types of soils on cotton and polyester/cotton fabric was determined by optical reflectance measurements. Gemini salts of LABS show improved cleaning performance compared to monovalent salts. Cleaning performance increases with increasing molecular weight of the diamine spacer group. In situ neutralization of LABS with organic diamines is a simple and efficient way to prepare anionic Gemini surfactants for industrial scale applications.     

Suspensions of Iron Oxide Nanoparticles Stabilized by Anionic Surfactants

Two common anionic surfactants, sodium oleate (SO) and sodium dodecyl benzene sulfonate (SDBS) were used to re‐suspend iron oxide nanoparticles in aqueous solutions. At certain SO concentrations, the SO formulations produced highly stable suspensions. In contrast, SDBS‐stabilized nanoparticles exhibited poor stability at all concentrations. The adsorption isotherm of SO on iron oxide nanoparticles revealed that stable suspensions were obtained when the equilibrium SO concentration (after adsorption) reached its critical micelle concentration (CMC). At this “optimal” condition, the maximum SO adsorption was reached, and the zeta‐potential of the particles was highly negative (～ ?50 mV). According to the SO isotherm, this optimal formulation coincided with the formation of a highly compact SO bilayer. The SDBS isotherm, on the other hand, revealed that SDBS is not strongly adsorbed on the surface of iron oxide nanoparticles and that is likely that a patchy, loosely packed bilayer, is formed on the surface of the iron oxide nanoparticles when the equilibrium SDBS concentration reaches its CMC. The DLVO theory confirmed the connection between formulation conditions and the corresponding stability. This works confirmed that the formation of a surfactant bilayer is an important element in producing stable nanoparticle suspensions with anionic surfactants. It was also confirmed that for anionic surfactants, electrostatic repulsions are an important factor in establishing an energy barrier against flocculation. This work also introduced two more elements into the design of nanoparticle suspensions. The first element is that, in order to ensure the best possible dispersion, the surfactant concentration in solution at equilibrium with the adsorbed surfactant should be close or slightly above its CMC. The second element is that the molecular structure of the surfactant should facilitate the formation of closely packed bilayers.     

4种新型氟碳表面活性剂

介绍了巨化集团技术中心最新开发的4种氟碳表面活性剂:3-三聚环氧六氟丙烷酰胺基丙基(2-亚硫酸) 乙基二甲基铵、3-三聚环氧六氟丙烷酰胺基丙基甜菜碱、8-3-9氟碳-碳氢柔桥混链双季铵、6-3_9氟碳柔桥混链双季铵。其临界胶束浓度CMC分别为1.14×10-4、1．12×10-3、4．93×10-4、2．78×10-4 mol／L,在临界胶束浓度时表面张力分别为19．0、22．0、20．9、22．7 mN／m,在质量分数0．1％时,表面张力分别为16．4、18．2、19．2、20．4 mN／m。分析了氟碳表面活性剂结构与性能的关系。     

无机电解质对十二烷基硫酸钠性质影响的研究

选择不同类型的无机电解质(NaCl、Na2SO4、Na3PO4、MgCl2、AlCl3),考察了电解质对十二烷基硫酸钠(SDS)表面张力、临界胶束浓度、润湿力、发泡力、乳化力的影响规律。实验表明,无机电解质对SDS的CMC影响显著,随着无机盐的加入,CMC降低,表面活性增强。当加入的氯化钠浓度达到0.3mol/L时,SDS的CMC降到了原来的十分之一,高价位离子对CMC影响大于低价位离子,同价位不同离子影响差别不大;SDS润湿性、乳化性、泡沫性能较好,加入电解质后,其润湿性增强,乳化性、泡沫高度和稳泡性降低。     

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。