奇碳链烷基芳基磺酸钠表面性能研究

本文是利用3种自制的高纯度奇碳链的炕基芳基磺酸钠,研究了芳环分别连在长烷基链2、6、8位、在25℃时对表面性质的影响。同时考察了温度对表面性质的影响。结果表明,在25~C时,随芳环向长烷基链中心移动,临界胶束浓度cmc升高,标准吸附自由能△G^0md二变小,但是,饱和吸附量Гmax随芳环向烷基链中间位置移动逐渐下降,分子独占面积Amin增大,临界胶柬浓度时的表面张力γmax～随吸附量的减少而降低,pC20增大。对于同一结构的烷基苯磺酸钠水溶液,随温度升高,cmc先减小后增大,△G^0ad更负,Гmax下降,γcmc降低,pC20增大。从分子结构的角度解释了Гmax～和γcmc等的变化规律,探讨了分子独占面积Гmax和γcmc的影响。     

非离子表面活性剂定量结构-性质相关性的研究

用量子化学参数来描述非离子表面活性剂的分子结构，研究分子的结构与临界胶束浓度(cmc)和表面张力(rcmc)的定量构效关系，建立了定量模型。其中，采用量子化学AM1方法和B3LYP／／6—31G^*方法计算了44个非离子表面活性剂化合物的电子结构特征，选取了7种量化参数和疏水链的烷基碳原子数，利用多元回归分析方法建立方程。回归结果表明，分子轨道能量(EHOMO)和电荷参数对cmc和rcmc影响较大，它们分别反映了非离子表面活性剂分子与水分子问的价键作用和静电作用。     

双子(Gemini)表面活性剂合成及研究进展

综述了阳离子型、阴离子型、非离子型和两性离子型四类双子表面活性剂的合成及研究进展,指出未来双子表面活性剂研究的主要方向为获得更高的表面活性、降低合成和使用成本、不同类型的表面活性剂协同强化、提高安全环保性和拓宽应用领域等。     

十二烷基苯磺酸钠水溶液聚集性质的研究

用滴体积法测出十二烷基苯磺酸钠（ＳＤＢＳ）稀水溶液的表面张力；然后求出其临界胶束浓度（ＣＭＣ）。同时通过溶液的电导率、吸收光谱以及荧光光谱测定求出其ＣＭＣ。这样测出的ＣＭＣ值为１．２～１．６×１０－３ｍｏｌ／Ｌ，与文献值相符。也研究了部分水解的聚丙烯酰胺（ＰＨＰＡＭ）对ＳＤＢＳ聚集性质的影响；发现ＳＤＢＳ的ＣＭＣ值随ＰＨＰＡＭ的加人而减少并且ＰＨＰＡＭ水溶液的粘度随ＳＤＢＳ的存在而急剧降低（类似盐效应）。这些方法与性质对强化采油（ＥＯＲ）是重要的。     

Enhancement of wetting properties of water-insoluble surfactantsvia solubilization

Water-insoluble surfactants generally show poor wetting behavior in the Draves skein wetting test. This does not appear to be due to high equilibrium or dynamic surface tension values, but to the presence of insoluble surfactant in the system. The replacement of a small percentage of the insoluble surfactant by a water-soluble one capable of solubilizing the former can produce a dramatic improvement in wetting behavior, even when the equilibrium or dynamic surface tension of the system is not significantly changed. Increase in the strength of the attractive interaction between the two surfactants generally improves the clarity of the system and decreases its wetting time.     

Diffusion-controlled Adsorption Kinetics of Surfactant at Air/Solution Interface

For the diffusion-controlled adsorption, the expression of dynamic surface adsorption Γ(t) was ob-tained by solving the diffusion equation. Two cases, i.e. the short and long time limits, were mainly d...     

表面活性剂在气/液界面上扩散控制的吸附动力学(英文)

For the diffusion-controlled adsorption, the expression of dynamic surface adsorption P（t） was ob- tained by solving the diffusion equation. Two cases, i.e. the short and long time limits, were mainly discussed in this paper. From the measured dynamic surface tension of aqueous surfactant sodium dodecyl sulfate （SDS） solutions at 25 ℃, the adsorption kinetics of SDS at air/solution interface was studied. It was proved that for both of the short and long time limits, the adsorption process of SDS was controlled by diffusion.     

聚烷基酚聚氧乙烯醚型表面活性剂的表面性能分析

合成了一系列不同聚合度的聚烷基酚聚氧乙烯醚(HHL)型非离子表面活性剂。通过红外光谱,核磁共振等仪器对其结构进行表征,用表面张力法对不同聚合度的合成产物的表面性能进行研究,并对不同聚合度的表面活性剂的物理化学参数进行理论分析。结果表明:三聚烷基酚聚氧乙烯醚型非离子表面活性剂较相应单体的烷基酚聚氧乙烯醚表面活性剂,表面活性和吸附能力有较大的提升。     

一种含全氟壬烯基硅表面活性剂的制备

研究了2-甲基-2-全氟壬烯氧基乙氧基羰基乙基甲基二聚乙氧基硅烷(Ⅴ)的制备方法和表面活性。以甲基丙烯酸-2-全氟壬烯氧基乙基酯(Ⅰ)和甲基二氯硅烷(Ⅱ)为原料,在氯铂酸催化下经过硅氢化反应得到2-甲基-2-全氟壬烯氧基乙氧基羰基乙基甲基二氯硅烷(Ⅲ),Ⅲ与聚乙二醇(Ⅳ)缩合反应得到非离子表面活性剂Ⅴ。用FTIR和MS对其结构进行了表征,优化了硅氢化反应工艺条件,测试了Ⅴ水溶液的表面张力和临界胶束浓度(CMC)。中间体Ⅲ的较优合成条件为:以四氢呋喃为溶剂,n(Ⅰ)∶n(Ⅱ)=1∶1.2,50℃下反应24 h,收率68.0%。表面活性剂Ⅴ水溶液的临界胶束质量浓度为0.22 g/L,此时的表面张力为19.5 mN/m,表明Ⅴ是高活性氟硅表面活性剂。     

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。     

饱和腰果酚阴-非离子型Gemini表面活性剂的合成与表面活性

以饱和腰果酚为原料,通过缩合、开环、羧甲基化反应合成两种具有新型化学结构的饱和腰果酚Gemini聚氧乙烯醚羧酸钠（GSCPEC-8和GSCPEC-10）,并研究其表面活性。FT-IR光谱和1H NMR证实饱和腰果酚Gemini聚氧乙烯醚羧酸钠结构。采用滴体积法测定了GSCPEC-8和GSCPEC-10水溶液的表面活性,结果表明：GSCPEC-8和GSCPEC-10水溶液的临界胶束浓度（cmc）分别为0.79mmol/L和0.69mmol/L,临界胶束浓度下的表面张力分别为36.56mN/m和39.37mN/m,最小单分子占有面积分别为1.9383nm2和1.1072nm2。GSCPEC水溶液的cmc值很低,具有较高的降低表面张力的效率;且随着EO基团的增加,形成胶束的能力与稳定性提高。     

季铵盐型阳离子型表面活性单体AMC16AB胶束化行为的研究

本文对季铵盐型阳离子表面活性单体2-丙烯酰胺基乙基十六烷基二甲基溴化铵（AMC16AB）的胶束化行为进行了深入的研究。使用紫外分光光度法测定了AMC16AB在水中的溶解度；同时采用表面张力法（环法）和电导滴定法测定其临界胶束浓度（CMC）及在浓度为CMC时的表面张力（γoc）。采用荧光探针法测定了不同浓度时（C〉CMC）AMC，6AB的胶束聚集数Nagg；并研究了AMC16AB浓度和外加盐浓度对Nagg的影响。实验结果表明表面活性单体AMC16AB在水中的溶解性强，但降低水表面张力的能力差，即表面活性差；与结构相同的一般表面活性单体相比，AMC16AB的CMC较低，Krafft点较低；AMC16AB的Nagg随浓度的增大而逐渐变大，随外加盐浓度增加开始时变化不大，当外加盐浓度达到临界值C★时，其胶束聚集数迅速增大。这些因素对AMC16AB胶束化行为的影响规律与普通的表面活性剂相似。     

一种非离子氟碳表面活性剂的合成及表征

以聚乙二醇、全氟丁酸为主要原料,采用直接酯化的方法,合成了一系列聚乙二醇系非离子型氟碳表面活性剂——聚乙二醇全氟丁酸酯(以单酯为主,且含有少量双酯),且对其红外光谱、表面张力、临界胶束浓度、浊点进行了测试。结果表明,该类氟碳表面活性剂具有很高的表面活性,同时,随PEG链段长度的变化,其表面张力、CMC值、浊点都发生规律性的变化。     

一种氟硅表面活性剂的合成及其表面活性

研究了2-甲基-2-全氟-2'-甲基-3'-氧代己酰氧基乙氧基羰基乙基甲基二聚氧乙烯基硅烷(Ⅴ)的制备方法和表面活性。以甲基丙烯酸-2-全氟-2'-甲基-3'-氧代己酰氧基乙基酯(Ⅰ)和甲基二氯硅烷(Ⅱ)为原料,0.5%Karsted催化剂存在下(以Ⅰ的质量计),发生硅氢化反应,得到2-甲基-2-全氟-2'-甲基-3'-氧代己酰氧基乙氧基羰基乙基甲基二氯硅烷(Ⅲ)。Ⅲ与聚乙二醇(Ⅳ)缩合反应得到非离子表面活性剂Ⅴ。用FTIR和MS对其结构进行了表征,优化了硅氢化反应工艺条件,测试了Ⅴ溶液的表面张力、临界胶束浓度(CMC)和处理玻璃后的疏水性能。以四氢呋喃为溶剂,中间体Ⅲ的较优合成条件为:n(Ⅰ)∶n(Ⅱ)=1.2∶1,50℃下反应28 h,化合物Ⅱ的转化率可达到68.2%。表面活性剂Ⅴ水溶液的CMC为0.52 g/L,临界表面张力γ_(CMC)为22.8 m N/m,用V的THF溶液处理玻璃后,玻璃表面具有很好的疏水性和较好的疏油性。     

磺酸盐型双基表面活性剂的合成与表面性能

以壬基酚和甲醛为原料,合成了一种新型的磺酸盐型双基表面活性剂(Gemini-A)。利用元素分析、红外光谱确定了Gemini-A的结构。研究了Gemini-A水溶液的润湿性,比较了Gemini-A与传统表面活性剂的增溶能力。试验结果表明,Gemini-A水溶液具有较低的表面张力(33.51 mN/m)和临界胶束浓度(0.141 mmol/L)及良好的润湿性,显示出了较好的表面性能,具有很强的增溶能力,是符合3次采油要求的表面活性剂。     

葡糖酰胺基四硅氧烷表面活性剂的合成及其表面活性

利用含有双胺基的四硅氧烷中的伯胺基与D-葡萄糖酸-δ-内酯酰胺化,仲胺基与低聚乙二醇甲醚缩水甘油醚烷基化的反应,制备了含葡糖酰胺基的四硅氧烷表面活性剂(Me3SiO)3Si(CH2)3NR(CH2)2NHCO(CHOH)4CH2OH,R=CH2CH(OH)CH2O(CH2CH2O)nCH3,n=1,2,3;并用IR和1HNMR对其结构进行了表征,用表面张力法测定其表面活性。结果表明:这种含葡糖酰胺基的四硅氧烷表面活性剂在水溶液中的临界聚集浓度cac小于10-4mol.L-1,最低表面张力γ小于21 mN.m-1;随着分子中乙氧基(EO)数的增加,cac明显增大,但γ变化很小。     

表面活性剂在气/液界面上的吸附动力学

在求解扩散方程的基础上,推导出了描述气 液界面吸附的动态吸附量Γ(t)表达式,并重点讨论了吸附的初始阶段和最终阶段两种极限情况。试验测定了25℃下表面活性剂C12E7[分子式CH3(CH2)11(OCH2CH2)7OH]水溶液的平衡及动态表面张力,结合理论推导,考察了C12E7在气 液界面的吸附过程。试验结果表明,气 液界面吸附过程在最初(极短时间)阶段是扩散控制,在吸附过程的后期(长时间)则出现了扩散 吸附混合控制。     

N-椰油酰基复合氨基酸钠的胶束化热力学特性的研究

用Wilhelmy法测定了实验室以废丝为原料制备的氨基酸型表面活性剂N-椰油酰基复合氨基酸钠溶液的平衡和动态表面张力,计算得出N-椰油酰基复合氨基酸钠溶液在30℃、35℃、40℃和45℃时的cmc值和其胶束形成的标准热力学函数ΔGθm、ΔHθm和ΔSθm,说明该胶束的形成是熵驱动过程。得到临界胶束浓度cmc与温度T的回归方程。胶束和反离子结合常数K0平均值为0.874 3。同时,研究了浓度及温度对扩散常数Da和Ea的影响及吸附过程模型。     

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.     

On the measurement of critical micelle concentrations of pure and technical-grade nonionic surfactants

The critical micelle concentrations (CMC) of nine commercial nonionic surfactants (Tween 20, 22, 40, 60, and 80; Triton X-100; Brij 35, 58, and 78) and two pure nonionics [C₁₂(EO)₅ and C₁₂(EO)₈] were determined by surface tension and dye micellization methods. Commercially available nonionic surfactants (technical grade) usually contain impurities and have a broad molecular weight distribution owing to the degree of ethoxylation. It was shown that the surface tension method (Wilhelmy plate) is very sensitive to the presence of impurities. Much lower CMC values were obtained with the surface tension method than with the dye micellization method (up to 6.5 times for Tween 22). In the presence of highly surfaceactive impurities, the air/liquid interface is already saturated at concentrations well below the true CMC, leading to a wrong interpretation of the break in the curve of surface tension (γ) vs. concentration of nonionic surfactant (log C). The actual onset of micellization happens at higher concentrations, as measured by the dye micellization method. Furthermore, it was shown that when a commercial surfactant sample (Tween 20) is subjected to foam fractionation, thereby removing species with higher surface activity, the sample yields almost the same CMC values as measured by surface tension and dye micellization methods. It was found that for monodisperse pure nonionic surfactants, both CMC determination methods yield the same results. Therefore, this study indicates that precaution should be taken when determining the CMC of commercial nonionic surfactants by the surface tension method, as it indicates the surface concentration of all surface-active species at the surface only, whereas the dye method indicates the presence of micelles in the bulk solution.