以混合中性-阳离子表面活性剂为模板合成MCM-48

本文首次将中性和阳离子表面活性剂混和(S^0S^+)形成胶束后,共同作为模板剂合成了立方相中孔分子筛,经此途径得到的中孔分子筛材料既具有MCM-48的立方结构,又能体现出更好的热稳定性。混合不同性质的表面活性剂作为模板剂,将是一种制备不同性能的中孔分子筛的有效易行的途径。     

混合表面活性剂模板法合成立方相介孔含钛氧化硅

自1992年Ｍｏｂｉｌ公司的Ｍ41Ｓ系列介孔氧化硅分子筛问世以来[1,2],借助表面活性剂液晶模板方法合成各种孔结构与不同大小孔径的硅基分子筛材料引起了人们的极大兴趣,目前多数工作仍然集中于六方相的介孔分子筛.具有双连续的三维交织立方排列孔道结构的ＭＣＭ48由于其孔道不易堵塞和良好的骨架结构稳定性[3,4],在催化、吸附和与其为载体的制备等方面具有独特的应用价值.但由于液晶模板形成立方相区的范围非常狭窄,相应的分子堆积比对模板剂分子几何结构要求较苛刻,采用单一表面活性剂为模板剂合成时,条件难以掌握,制备ＭＣＭ48十分困难.Ｈ…     

混合阳离子-非离子表面活性剂为模板剂合成含沸石次级结构单元的介孔分子筛

利用混合阳离子-非离子表面活性剂为模板剂采用两步晶化法合成了孔壁具有沸石次级结构单元的介孔分子筛，通过XRD、N2吸附-脱附、FT-IR以及异丙苯裂解探针反应等手段对样品进行了表征。结果表明，合成的介孔材料在结构上与相应的M41S材料类似，无微孔沸石相的存在。立方介孔材料具有较高的热稳定性和水热稳定性，在催化异丙苯裂解反应中，六方介孔材料的催化活性明显高于相似条件下用单一表面活性剂为模板剂合成的含沸石次级结构单元的六方介孔材料。     

以新型模板方法合成中孔SiO_2分子筛(英文)

以廉价、生物可降解的两性表面活性剂十四烷基甜菜碱作为模板剂,以正硅酸乙酯为硅源,在酸性条件下成功地合成了具有螺旋状孔道结构的 SiO_2中孔分子筛 .热重表征结果说明,采用溶剂萃取（乙醇的水溶液为萃取剂）的方法,近乎 100％的模板剂可以脱除回收 .     

以新型模板方法合成中孔SiO2分子筛

以廉价、生物可降解的两性表面活性剂十四烷基甜菜碱作为模板剂,以正硅酸乙酯为 硅源,在酸性条件下成功地合成了具有螺旋状孔道结构的SiO2中孔分子筛.热重表征结果说 明,采用溶剂萃取（乙醇的水溶液为萃取剂）的方法,近乎100％的模板剂可以脱除回收.     

超分子模板法合成层状中孔结构氧化铝

利用烷基硫酸钠作为模板剂在室温下合成了层状中孔结构氧化铝,考察了表面活性剂碳链长度和表面活性剂混合比例对层状氧化铝中孔相结构参数的影响.当使用单一表面活性剂作为模板剂时,层状中孔结构氧化铝的层间距d及其层状结构的长程有序度随着表面活性剂碳链长度的增加而增加;若使用C₈H₁₇SO₄Na与C₁₄H₂₉SO₄Na混合表面活性剂作为混合模板剂,当C₁₄H₂₉SO₄Na摩尔分数x处在0～0.5时,层间距基本恒定,接近于具有二者平均碳链长度(n=11)的单一表面活性剂作为模板剂时的情形;当x>0.5时,层间距随x的增大而逐渐增大.通过提出的混合表面活性剂在无机层中的分子排列结构模型对该结果做了解释.     

非离子型表面活性剂在SiO2凝胶中的造孔作用

以非离子型表面活性剂C13EO9(或简写为AEO9)为模板剂,在强酸性的乙醇-水体系中通过溶胶-凝胶途径合成SiO2分子筛。结果表明,经焙烧去除模板剂以后的分子筛具有双孔分布的特征,孔径主要集中在2.56nm和13.95nm。经高分辨电镜(HRTEM)和X射线衍射(XRD)测试分析,前者呈有序排列,类似于MSU系列分子筛的孔道结构,而后者则呈无序的排列,它是由胶体粒子聚集而形成的颗粒间孔,并与在相同条件下不加AEO9制备的无定形SiO2凝胶以及用离子型表面活性剂十六烷基三甲基溴化铵(CTAB)代替AEO9为模板剂制备的分子筛进行了比较,二者的孔道结构分别呈无序排列和六方有序排列的单一孔分布特征。     

模板技术制备单块介孔分子筛

模板技术与溶胶 -凝胶过程结合是合成介孔分子筛的有效方法 .模板通常采用表面活性剂在一定条件下自组装形成超分子结构 ,在不同条件下 ,此超分子结构具有不同聚集形态 ,合成出的介孔分子筛也具有不同的孔道排列方式 [1～ 4 ] .溶胶 -凝胶过程是通过硅源体的水解缩合并缓慢蒸发除去溶剂实现的 .此过程及产物受体系的 p H值影响很大 .在碱性体系中制备的介孔材料通常为粉末状 ,不利于实际应用 ,因此人们更加重视合成具有规则外形的介孔材料[5] .目前报道大多是在酸性体系中制备不同形状的介孔材料 [6～ 12 ] .有关合成单块介孔分子筛的报道…     

以伯胺为模板剂合成含铁介孔分子筛FeHMS

以非离子型表面活性剂伯胺为模板剂合成了含铁介孔分子筛FeHMS,并对其结构和形态进行了表征。发现FeHMS的颗粒比SiHMS小,粒子表面更为光滑。除了2.5nm的介孔外,FeHMS还原10nm左右的孔。FeHMS介孔分子筛在脱除模板剂之前,铁主要处于四面体配位状态的骨架位,经焙烧脱除模板剂之后,部分铁由骨架位迁移到孔壁表面。用酸化的乙醇溶液抽提脱除模板剂,能更有效地让铁保留在四面体配位状态的骨架位上。高温脱除模板剂后,孔壁表面的铁物种处于一种高分散的状态。此外还研究了HMS类介孔分子筛材料的水热稳定性,发现铁的引入可改善介孔分子筛材料的水热稳定性。     

以伯胺为模板剂合成含铁介孔分子筛FeHMS

以非离子型表面活性剂伯胺为模板剂合成了含铁介孔分子筛FeHMS,并对其结构和形态进行了表征。发现FeHMS的颗粒比SiHMS小,粒子表面更为光滑。除了2.5nm的介孔外,FeHMS还原10nm左右的孔。FeHMS介孔分子筛在脱除模板剂之前,铁主要处于四面体配位状态的骨架位,经焙烧脱除模板剂之后,部分铁由骨架位迁移到孔壁表面。用酸化的乙醇溶液抽提脱除模板剂,能更有效地让铁保留在四面体配位状态的骨架位上。高温脱除模板剂后,孔壁表面的铁物种处于一种高分散的状态。此外还研究了HMS类介孔分子筛材料的水热稳定性,发现铁的引入可改善介孔分子筛材料的水热稳定性。     

用双表面活性剂为共模板合成中孔分子筛MCM-48

利用水热法以非离子表面活性剂聚乙二醇辛基苯基醚和阳离子表面活性剂十六烷基三甲基溴化铵为共模板合成了中孔分子筛MCM-48.实验中发现利用较强的范德华力和氢键,聚乙二醇辛基苯基醚可在很大程度上降低合成MCM-48所需阳离子表面活性剂的用量,且利于制备有序性好、骨架聚合度高、稳定性好的MCM-48.通过调节聚乙二醇辛基苯基醚与十六烷基三甲基溴化铵的比例,可得到不同物相结构的分子筛.     

Mixed micelle behavior of Pluronic L64 and Triton X-100 with conventional and dimeric cationic surfactants

The mixed micellar properties of a triblock copolymer, Pluronic L64, (EO)13(PO)30(EO)13, and a nonionic surfactant, Triton X-100, in aqueous solution with conventional alkyl ammonium bromides and their dimeric homologues were investigated with the help of fluorescence and cloud point measurements. The composition of mixed micelles and the interaction parameter, beta, evaluated from the critical micelle concentration (cmc) data for different mixtures using Rubingh's and Motomura's theories are discussed. It has been observed that the mixed micelle formation between monomeric/dimeric alkyl ammonium bromides and L64 was due to synergistic interactions which increase with the increase in hydrophobicity of the cationic component. On the other hand, synergistic mixing was observed in the mixed micelles of Triton X-100 and monomeric cationic surfactants, the magnitude of which decreases slightly with the increase in hydrophobicity of the cationic component. Antagonistic interactions were observed in the case of Triton X-100 and dimeric cationic surfactants.     

Mixed micellar properties of cationic trimeric-type quaternary ammonium salts and anionic sodium n-octyl sulfate surfactants

The properties of quaternary ammonium salt-type cationic trimeric surfactants (m-2-m-2-m, m represents the carbon atom number in alkyl chain lengths of 8, 10, and 12) and oppositely charged anionic monomeric surfactant, sodium n-octyl sulfate (SOS), were characterized by employing several techniques such as static surface tension, fluorescence spectroscopy, and dynamic light-scattering measurements. The critical micelle concentrations (cmc) of m-2-m-2-m were much lower than those of the corresponding dimeric and monomeric surfactants, and decreased with increasing chain length. The addition of SOS to m-2-m-2-m solutions resulted in a further decrease of the cmc. The mixed surfactants showed higher efficiencies in lowering the surface tension than the individual surfactants. The fluorescence measurements suggested the formation of mixed micelles with a hydrophobic environment in the solutions even at lower concentrations. The dynamic light-scattering study indicated the presence of two different kinds of aggregates with different hydrodynamic diameters. The larger one was attributed to the mixed micelle of m-2-m-2-m and SOS. These results indicated a decline of the electrostatic repulsion between cationic head groups through the incorporation of anionic surfactant into the mixed surfactants.     

表面活性剂双水相的性质及其应用 Ⅰ. 表面活性剂双水相的微环境性质

阴、阳离子表面活性剂混合体系, 在一定浓度及混合比范围内, 可以形成两个互不相溶、平衡共存的水相, 称为表面活性剂双水相。其中阳离子表面活性剂过量的双水相体系, 称为阳离子双水相。本文分别以芘和罗丹明B作为探针, 用荧光探针法研究了摩尔比为1.6:1的C12NE和SDS混合体系成形成的阳离子双水相,测定其上层和下层的胶束微环境的极性和微粘度, 取得了有意义的结果。     

Interaction between biosurfactant surfactin and cationic surfactant cetyl trimethyl ammonium bromide in mixed micelle

An anionic/cationic mixed surfactant aqueous system of surfactin and cetyl trimethyl ammonium bromide (CTAB) at different molar ratios was studied by surface tension and fluorescence methods (pH 8.0). Various parameters that included critical micelle concentration (cmc), micellar composition (X ₁), and interaction parameter (β ^m) as well as thermodynamic properties of mixed micelles were determined. The β ^m was found to be negative and the mixed system was found to have much lower cmc than pure surfactant systems. There exits synergism between anionic surfactin and cationic CTAB surfactants. The degree of participation of surfactin in the formation of mixed micelle changes with mixing ratio of the two surfactants. The results of aggregation number, fluorescence anisotropy, and viscosity indicate that more packed and larger aggregates were formed from mixed surfactants than unmixed, and the mixed system may be able to form vesicle spontaneously at high molar fraction of surfactin.     

Foaming and foam stability for mixed polymer-surfactant solutions: effects of surfactant type and polymer charge

Solutions of surfactant-polymer mixtures often exhibit different foaming properties, compared to the solutions of the individual components, due to the strong tendency for formation of polymer-surfactant complexes in the bulk and on the surface of the mixed solutions. A generally shared view in the literature is that electrostatic interactions govern the formation of these complexes, for example between anionic surfactants and cationic polymers. In this study we combine foam tests with model experiments to evaluate and explain the effect of several polymer-surfactant mixtures on the foaminess and foam stability of the respective solutions. Anionic, cationic, and nonionic surfactants (SDS, C(12)TAB, and C(12)EO(23)) were studied to clarify the role of surfactant charge. Highly hydrophilic cationic and nonionic polymers (polyvinylamine and polyvinylformamide, respectivey) were chosen to eliminate the (more trivial) effect of direct hydrophobic interactions between the surfactant tails and the hydrophobic regions on the polymer chains. Our experiments showed clearly that the presence of opposite charges is not a necessary condition for boosting the foaminess and foam stability in the surfactant-polymer mixtures studied. Clear foam boosting (synergistic) effects were observed in the mixtures of cationic surfactant and cationic polymer, cationic surfactant and nonionic polymer, and anionic surfactant and nonionic polymer. The mixtures of anionic surfactant and cationic polymer showed improved foam stability, however, the foaminess was strongly reduced, as compared to the surfactant solutions without polymer. No significant synergistic or antagonistic effects were observed for the mixture of nonionic surfactant (with low critical micelle concentration) and nonionic polymer. The results from the model experiments allowed us to explain the observed trends by the different adsorption dynamics and complex formation pattern in the systems studied.     

Micellization and mixed micellization of cationic gemini (dimeric) surfactants and cationic conventional (monomeric) surfactants: Conductometric,dye solubilization,and surface tension studies

In the present study, we have investigated the self-association, mixed micellization, and thermodynamic studies of a cationic gemini (dimeric) surfactant, hexanediyl-1,6-bis(dimethylcetylammonium bromide (16-6-16)) and a cationic conventional (monomeric) surfactant, cetyltrimethylammonium bromide (CTAB). The critical micelle concentration (CMC) of pure (16-6-16 and CTAB) and mixed (16-6-16+CTAB) surfactants was measured by electrical conductivity, dye solubilization, and surface tension measurements. The surface properties (viz., C₂₀ (the surfactant concentration required to reduce the surface tension by 20 mN/m), Π_CMC (the surface pressure at the CMC), Γ_max (maximum surface excess concentration at the air/water interface), A_min (the minimum area per surfactant molecule at the air/water interface), etc.) of micellar (16-6-16 or CTAB) and mixed micellar (16-6-16+CTAB) surfactant systems were evaluated. The thermodynamic parameters of the micellar (16-6-16 and CTAB) and mixed micellar (16-6-16+CTAB) surfactant systems were also evaluated.     

Counterion binding on mixed anionic/cationic micelles

Measurements of counterion binding in mixtures of surfactant aqueous solutions have been performed to study the structure of the anionic/cationic mixed micelle/solution interface. The mixtures studied were SDS/DDAC and STS/TDPC. The binding of chloride and sodium ions to mixed anionic/cationic micelles was measured using ion-specific electrodes. Counterion binding was found to be strongly dependent on the molar ratio of surfactants present. The mixed micelle/solution interface includes the headgroups of both surfactants and counterions of surfactant in excess. The addition of oppositely charged surfactant caused an increasing dissociation of counterions.     

Micellization of dissymmetric cationic gemini surfactants and their interaction with dimyristoylphosphatidylcholine vesicles

The micellization process of a series of dissymmetric cationic gemini surfactants [CmH2m+1(CH3)2N(CH2)6N(CH3)2C6H13]Br2 (designated as m-6-6 with m = 12, 14, and 16) and their interaction with dimyristoylphosphatidylcholine (DMPC) vesicles have been investigated. In the micellization process of these gemini surfactants themselves, critical micelle concentration (cmc), micelle ionization degree, and enthalpies of micellization (DeltaHmic) were determined, from which Gibbs free energies of micellization (DeltaGmic) and entropy of micellization (DeltaSmic) were derived. These properties were found to be influenced significantly by the dissymmetry in the surfactant structures. The phase diagrams for the solubilization of DMPC vesicles by the gemini surfactants were constructed from calorimetric results combining with the results of turbidity and dynamic light scattering. The effective surfactant to lipid ratios in the mixed aggregates at saturation (Resat) and solubilization (Resol) were derived. For the solubilization of DMPC vesicles, symmetric 12-6-12 is more effective than corresponding single-chain surfactant DTAB, whereas the dissymmetric m-6-6 series are more effective than symmetric 12-6-12, and 16-6-6 is the most effective. The chain length mismatch between DMPC and the gemini surfactants may be responsible for the different Re values. The transfer enthalpy per mole of surfactant within the coexistence range may be associated with the total hydrophobicity of the alkyl chains of gemini surfactants. The transfer enthalpies of surfactant from micelles to bilayers are always endothermic due to the dehydration of headgroups and the disordering of lipid acyl chain packing during the vesicle solubilization.