表面活性剂与高分子链混合体系的模拟

计算机模拟了高分子链对表面活性剂胶束形成过程的影响，以及高分子链构象性质随胶束化过程的变化.结果表明,当高分子链与表面活性剂之间的相互作用强度超过临界值后，高分子链的存在有利于表面活性剂胶束的形成.临界聚集浓度（CAC）与临界胶束浓度（CMC）的比值CAC/CMC随高分子链长的增大和相互吸引作用的增强而减小.在CAC之前，高分子链与表面活性剂分子只有动态的聚集；但在CAC之后，表面活性剂胶束随表面活性剂浓度X的增加而增大，并静态地吸附在高分子链上，形成表面活性剂/高分子聚集体.随着表面活性剂分子的加入，高分子链的均方末端距和平均非球形因子先保持恒定；从X略小于CAC开始， 和快速减小，至极小值后又逐渐增大.模拟结果支持高分子链包裹在胶束表面的实验模型.     

共聚物/表面活性剂体系微观与宏观粘度

高分子与表面活性剂的相互作用，无论从基础研究还是应用研究均很有意义＊．表面活性剂和高分子相互作用往往可以使高分子链的的象变化，例如通过生成分子缔合复合作问（associatedcomPleX），改变高分子链的静电相互作用，可引起高分子链的舒展和卷曲．另一方面，高分子也影响表面活性剂的物理化学性质．例如，溶液表面张力、粘度、电导、表现临界胶束浓度（＊＊C）和聚集数（＊叫等物理参数。‘］．在实用方面，在高分子和表面活性剂相互作用的复合体中，表面活性剂分子排列接近生物膜结构，可作为模拟生物酶催化的模型体系问．由超高分…     

高分子表面活性剂在固/液界面上的吸附形态

采用紫外光谱、XPS研究了羧甲基纤维素型高分子表面活性剂在硅胶 /水界面上的吸附形态 ,结果表明随着高分子表面活性剂溶液浓度增大 ,分子在硅胶表面的吸附由单层逐渐变为多层 ,生成半胶束结构 .     

正负离子表面活性剂与两性表面活性剂的相互作用

本文研究正负离子表面活性剂与两性表面活性剂混合水溶液的表面性质, 以及两性表面活性剂对正负离子裘面活性剂溶解度的影响。结果表明: (1) 两性表面活性剂的加溶作用,有助于正负离子表面活性剂的溶解; (2) 加入两性表面活性剂的量适当, 混合溶液基本保持原正负离子表面活性剂的表面活性; (3) 正负离子表面活性剂与两性表面活性剂在表面层和胶团中分子间的相互作用比正负离子表面活性剂与非离子表面活性剂分子间的相互作用稍强HC-FC正负; 离子表面活性剂与两性表面活性剂混合体系在表面层中有可能形成双分子或多分子层结构。     

CMC系列高分子表面活性剂的胶束形态

高分子表面活性剂分子量高 ,分子中兼具亲水和疏水链段 ,在选择性溶剂水中同小分子表面活性剂一样 ,可形成疏水链段为核心、亲水链段为外壳的胶束结构 ,但高分子量又使其表现出许多不同于低分子表面活性剂的形态特征 ,如胶束的多种形态、尺寸分布多分散性等等 ,而这些形态特征对高分子表面活性剂的界面活性、增粘、乳化等性能有决定性的影响．结构规整的嵌段或接枝共聚物在选择性溶剂中的分子聚集形态已有研究 ［１,２］,亲水亲油性的高分子表面活性剂在水溶液中由于结构复杂、水溶液中氢键作用及静电作用力等因素造成的困难 ,因而研究较少…     

高分子表面活性剂的合成

介绍了高分子表面活性剂的合成方法及其不同于低分子表面活性剂的特点,重点从离子聚合、活性自由基聚合、缩合聚合、开环聚合、高分子化学反应、自由基胶束聚合等角度综述了近几-来高分子表面活性剂的合成研究进展.     

聚氨酯高分子表面活性剂的研究进展

在乳液聚合中,传统的小分子表面活性剂发挥着非常关键的作用,但是它们容易在漆膜中发生迁移,最终降低涂膜的耐水性;而高分子表面活性剂的使用,可以较好的避免表面活性剂的解析及其在膜中的迁移.其中,聚氨酯类的高分子表面活性剂由于具有良好的表面活性、优异的耐寒性、弹性、高光泽以及其软硬度可随温度变化,耐有机溶剂性好等优点, 已经成为研究的热点.本文综述了近几年来,聚氨酯表面活性剂的种类、合成以及应用的进展,并对其进行了讨论.     

水性环氧树脂乳液的研制

采用环氧树脂和非离子型表面活性剂反应合成了反应型水性环氧树脂乳化剂，将具有表面活性的分子链段引入到环氧树脂分子链中，用相反转技术制备水性环氧树脂乳液。研究了乳化剂合成时表面活性剂分子量、环氧树脂分子量，乳化剂构型、乳化剂浓度和乳化剂合成的反应时间对乳液稳定性的影响。     

羧甲基纤维素—十二烷基醇聚氧乙烯醚丙烯酸酯共聚物表面活性剂在水溶 …

采用动态激光光散射及环境扫描电镜研究了羧甲基纤维素型高分子表面活性剂在水溶液中的胶束形态。结果表明，共聚物在水溶液中的形态完全不同于羧甲基纤维素分子亲水疏水链段的引入，使共聚物分子聚集成了以疏水链段为核心的棍状胶束结构。高分子表面活性剂水溶液体系的归一化一级相关函数不符合单指数衰减，表明胶束形态的多分散性。在０．００５％￣１％浓度范围内，胶束粒大大小均分布的两个区域，随共聚物浓度增大，低粒径区保持     

利用高分子多基元协同效应增强脂质体稳定性的研究

通过合成接枝胆固醇的壳聚糖水溶性高分子，并利用所接枝胆固醇的插膜能力，诱导高分子贴附于脂质体表面，形成高分子-脂质体复合物.研究发现，壳聚糖水溶性高分子可以起到屏蔽膜表面电荷的作用，同时该体系利用高分子链上多位点修饰的疏水基团与磷脂分子之间的疏水作用和高分子多基元之间共价连接的协同效应，增强了脂质体的抗融合及抗表面活性剂能力.该复合策略制备过程简便快捷，在体外实验中已展现出良好的稳定性，在长循环药物递送方面具有潜在的应用.     

新型腰果酚双子表面活性剂的合成及表面活性

以天然生物质腰果酚、1,3-二溴丙烷及氯磺酸为原料,通过醚化、磺化及中和三步反应合成了一类新型的腰果酚基磺酸盐双子(Gemini)表面活性剂.采用傅立叶转换红外光谱仪和核磁共振谱仪表征了产物的结构;采用滴体积法测定了腰果酚Gemini表面活性剂的表面张力,研究了水溶液的表面性质,并与相应的单基腰果酚基磺酸盐表面活性剂进行了对比.结果表明:腰果酚Gemini表面活性剂水溶液的临界胶束浓度(cmc)为6.20×10-2 mmol.L-1,远小于相应的单基腰果酚表面活性剂水溶液的cmc(8.40mmol.L-1);其临界表面张力γcmc为36.92mN.m-1,与单基腰果酚表面活性剂水溶液的相近(γcmc为38.41mN.m-1).与此同时,腰果酚Gemini表面活性剂水溶液的最小分子截面积Amin为0.27nm2,比相应的单基表面活性剂水溶液的小得多.     

Adsorption of sodium dodecyl sulfate at the hydrophobic solid/aqueous solution interface in the presence of poly(ethylene glycol): dependence upon polymer molecular weight

The polar orientation and degree of conformational order of sodium dodecyl sulfate (SDS) adsorbed at the hydrophobic octadecanethiol/aqueous solution interface in the presence of poly(ethylene glycol) (PEG) has been investigated as a function of the surfactant concentration and the molecular weight of the polymer. Sum frequency generation (SFG) vibrational spectroscopy was employed to obtain spectra of interfacial surfactant; weak SFG signals from interfacial polymer were also detected for polymer molecular weights of 900 and above. The phase of the SFG spectra indicated that both the surfactant and polymer had a net orientation of their CH2 and/or CH3 groups toward the hydrophobic surface. Spectra of SDS in the presence of mixed polymer/surfactant solutions showed increasing conformational order as the surfactant concentration was raised. At the lowest surfactant concentrations, the spectra of SDS were weaker in the presence of the polymer than in its absence. All PEG molecular weights investigated, with the exception of PEG 400, gave rise to significant inhibition of ordered surfactant adsorption below the critical micelle concentration. The greatest inhibitory effect was noted for PEG 900. Probing interfacial PEG specifically through the use of perdeuterated SDS revealed that the polymer spectral intensity decreased monotonically as the surfactant concentration was increased for all polymer molecular weights where a PEG spectrum was apparent. These findings are interpreted in terms of the displacement of preadsorbed polymer as the surfactant concentration increases. This result is compatible with observations of adsorption from SDS/PEG solutions at solid/solution and solution/air interfaces made using other techniques.     

Marangoni flow in micro-channels

A novel electrochemical method for driving fluids in micro-channels is presented. The principle is based upon the onset of Marangoni flow along the interface between an aqueous solution (mobile phase) and an organic electrolyte polymer gel coated on the inner walls of the micro-channel. The gradient of surface tension responsible for the fluid motion arises from local changes in the surface charge. The excess charge is determined by the ionisation of surfactant species at the gel coating|aqueous electrolyte interface which is effectively dependent on the Galvani potential difference. Potential differences of less than a volt between two closely spaced silver band electrodes along the micro-channel can generate zones of high and low surface tension, promoting the motion of the aqueous electrolyte.     

Adsorption of Triton X-100 and cetyltrimethylammonium bromide mixture with ethanol at nylon-6–solution interface with regard to nylon-6 wettability: II. Work of adhesion and activity of surfactants at interfaces

On the basis of the values of the surface tension of the aqueous solutions of the Triton X-100 and CTAB mixture with ethanol, the surface tension of nylon-6 and the nylon-6–solution interfacial tension, the activity of the surfactant mixture and ethanol at the nylon-6–solution interface was calculated and compared to that at the solution–air one. For these calculations, the Sprow and Prausnitz equation was applied. The obtained values of the activity were used for the calculations of the work of adhesion of the solution to the polymer surface. The values of the work of adhesion obtained in this way were compared to those determined from the Young–Dupre equation by using the contact angle values of the aqueous solutions of the TX-100 and CTAB mixture with ethanol measured on the nylon-6 surface. The changes of the work of adhesion determined from the Young–Dupre equation were also considered as a function of the surface tension of the solution, its polar component and the interfacial interaction parameter.     

聚合物调控氧化钛层柱蒙脱石的结构和性能研究

为了改善氧化钛层柱蒙脱石的结构性能,以长链聚合物-端氨基聚甲基环氧乙烷(PPO-D-2000)为结构调节剂,调控合成了聚合物-氧化钛层柱蒙脱石材料。采用X射线粉末衍射、红外、拉曼光谱、TG/DSC、TEM和BET等手段进行了结构表征。结果表明,相比于小分子量表面活性剂而言,长链聚合物不仅能显著提高氧化钛层柱蒙脱石中的二氧化钛含量,而且比表面积比单独氧化钛柱撑蒙脱石增加了约13%,达到241.52m2/g,尤其是孔径、孔体积等孔道结构参数增加一倍左右。将合成的柱撑蒙脱石材料应用于对水中甲基橙的吸附和光催化性能研究表明,聚合物的调控作用能提高氧化钛层柱蒙脱石的吸附能力,光催化效率也有所改善。因此,聚合物对优化无机层柱粘土材料结构、改善吸附和催化性能具有良好的调控作用,为发展环境催化材料提供了新的途径。     

Shape-tunable polymer nodules grown from liposomes via ring-opening metathesis polymerization

A new inisurf (acting as surfactant and initiator) molecule for ring-opening metathesis polymerization (ROMP) was synthesized and used in aqueous solution in order to control the size and shape of polymer nodules grown from liposomes. Nodules were observed to grow in size with conversion of monomer, and depending on the monomer used, they adopted either a spherical or comet-like shape. Here, we investigate polymer production from a liposome surface. We use a hydrophobic derivative of the Grubbs catalyst positioned at the liposome surface to allow for ROMP of monomers dissolved in the aqueous outer phase. We obtain nodules of polymer that can grow up to tens of micrometers, unveiling new efficient possibilities of polymerization from a membrane in an aqueous solution.     

Studies on the interactions between anionic surfactants and polyvinylpyrrolidone: Surface tension measurement, 13C NMR and ESR

 The interaction between anionic surfactants and polyvinylpyrrolidone (PVP) are investigated using ¹³C NMR, ESR spectroscopy and surface tension measurements at the air/water interface. The behavior of single-chained surfactant, sodium dodecyl sulphonate (AS), is compared with that of the double-chained surfactant, sodium bis(2-ethylhexyl) phosphate (NaDEHP). The results showed that a surfactant–polymer complex of “necklace and head structure” is formed in AS aqueous solutions in the presence of PVP due to the hydrophobic interaction between PVP and AS. The AS micelles nucleate on the polymer hydrophobic sites, and the mobility of the AS head groups is not affected. But, for NaDEHP surfactant, it was found that PVP is little effective in influencing the monomer–micelle equilibrium and no surfactant– polymer complex formed in the NaDEHP aqueous solution. Received: 8 May 1996 Accepted: 14 August 1997     

Optical and surface morphological properties of polarizing films fabricated from a chromonic dye by the photoalignment technique

The inherent chromonic lyotropic liquid crystalline properties of a dye have been manipulated to fabricate multi-axial micropolarizing thin films by means of the photoalignment technique. The dye aqueous solution is deposited on a photopatterned polymer film to result in the macroscopic alignment of the dye molecules, followed by drying at ambient temperature. The solid polarizing dye layers thus produced exhibit very a high contrast ratio and degree of polarization in the region of visible light. Addition of a small amount of surfactant to the dye solution is a prerequisite for the generation of a nematic chromonic phase and for the formation of homogeneous thin dye layers on the polymer film. The correlation between the optical and surface morphological properties of the dye layers is discussed.     

Synergistic effects in flows of mixtures of wormlike micelles and hydroxyethyl celluloses with or without hydrophobic modifications

This work presents experimental results on simple shear and porous media flow of aqueous solutions of two hydroxyethyl celluloses (HEC) and two hydrophobically modified hydroxyethyl celluloses (HMHEC) with different molecular weights. Mixtures of these polymers with a cationic surfactant, cetyltrimethylammonium p-toluenesulfonate (CTAT) were also studied. Emphasis was given to the range of surfactant concentrations in which wormlike micelles are formed. The presence of hydrophobic groups, the effect of the molecular weight of the polymers, the surfactant and polymer concentrations, and the effect of the flow field type (simple shear versus porous media flow) were the most important variables studied. The results show that the shear viscosity of HEC/CTAT solutions is higher than the viscosities of surfactant and polymer solutions at the same concentrations, but surface tension measurements indicate that no complex formation occurs between CTAT and HEC. On the other hand, a complex driven by hydrophobic interactions was detected by surface tension measurements between CTAT and HMHEC. In this case, the viscosity of the mixture increases significantly more (up to four orders of magnitude at high CTAT concentrations) in comparison with HEC/CTAT aqueous solutions. Increments in the molecular weight of the polymers increase the interaction with CTAT and the shear viscosity of the solution, but make phase separation more feasible. In porous media flow, the polymer/CTAT mixtures exhibited higher apparent viscosities than in simple shear flows. This result suggests that the extensional component of the flow field in porous media flows leads to a stronger interaction between the polymer and the wormlike micelles, probably as a consequence of change of conformation and growth of the micelles.     

Adsorption of polyelectrolyte/surfactant mixtures at the air-solution interface: poly(ethyleneimine)/sodium dodecyl sulfate

Neutron reflectivity and surface tension have been used to characterize the adsorption of the polyelectrolyte/ionic surfactant mixture of poly(ethyleneimine) (PEI) and sodium dodecyl sulfate (SDS) at the air-water interface. The surface tension behavior and adsorption patterns show a strong dependence upon the solution pH. However, the SDS adsorption at the interface is unexpectedly most pronounced when the pH is high (when the polymer is essentially a neutral polymer) and when the polymer architecture is branched rather than linear. For both the branched and the linear PEI polymer/surfactant complex formation results in a significant enhancement of the amount of SDS at the interface, down to surfactant concentrations approximately 10(-6) M. For the branched PEI a transition from a monolayer to a multilayer adsorption is observed, which depends on surfactant concentration and pH. In contrast, for the linear polymer, only monolayer adsorption is observed. This substantial increase in the surface activity of SDS by complexation with PEI results in spontaneous emulsification of hexadecane in water and the efficient wetting of hydrophobic substrates such as Teflon. In regions close to charge neutralization the multilayer adsorption is accentuated, and more extensively ordered structures, giving rise to Bragg peaks in the reflectivity data, are evident.