添加剂对含羟基基团Gemini表面活性剂自组装行为的影响

发布时间：2018-06-19 06:33

本文选题：Gemini表面活性剂 + 蠕虫胶束　；参考：《江南大学》2017年硕士论文

【摘要】：Gemini表面活性剂是近几年来倍受关注的两亲分子,其新颖且多样化的分子结构使其具有很多独特的性质。Gemini表面活性剂在头基或靠近头基处引入联接链,能够有效地控制Gemini表面活性剂单元分子离子头基间的距离,使其烷烃链密度和头基电荷密度均发生明显改变。头基电荷密度的改变,必然对溶液中反离子的作用更加敏感。本论文选取同分异构体的有机盐及系列具有相反电荷的表面活性剂分别与季铵盐阳离子Gemini表面活性剂复配,系统地研究了Gemini表面活性剂在构筑蠕虫胶束的过程中,有机盐及相反电荷表面活性剂结构的微小变化对蠕虫胶束的形成和生长及溶液粘弹性的影响,相关结果对于深入了解Gemini表面活性剂的自组装特性及总结分子间相互作用规律有着重要科学意义。主要研究内容如下:1.利用稳态和动态剪切流变实验手段,研究了三种同分异构体的有机盐,邻羟基苯甲酸钠(o-ph-ONa)、间羟基苯甲酸钠(m-ph-ONa)和对羟基苯甲酸钠(p-ph-ONa)对2-羟基-三亚甲基-α,ω-双十二烷基三甲基溴化铵(12-3(OH)-12)自组装行为的影响即盐/12-3(OH)-12复配体系中蠕虫胶束形成和生长的影响。通过表面张力法和1H-1H 2D NOESY法来验证有机盐和表面活性剂12-3(OH)-12相互作用的方式和程度。研究结果发现,三种有机盐均与12-3(OH)-12分子发生相互作用,有效促进了12-3(OH)-12溶液中蠕虫胶束的形成。有机盐分子结构的微小变化,对Gemini表面活性剂蠕虫胶束的形成和生长产生的影响差别较大,并最终导致溶液粘弹性的差异。其中,o-ph-ONa更易促进12-3(OH)-12分子形成蠕虫胶束,m-ph-ONa次之,而p-ph-ONa促进体系形成蠕虫胶束的能力最弱。2.合成了一系列新型羧酸盐阴离子Gemini表面活性剂SL-n-SL(n=3,6,10),利用质谱、氢谱对其结构进行了确证。通过Py荧光探针法和表面张力法测定了三种羧酸盐阴离子Gemini表面活性剂在25 oC下的表面活性,SL-n-SL(n=3,6,10)的cmc值分别是0.29mmol·L-1、0.058 mmol·L-1和0.012 mmol·L-1,表明三种表面活性剂在水溶液中的聚集能力很强,且强度随联接链的增长而变大;γcmc值分别是31.96 mN?m-(16)、36.18 mN?m-(16)和36.27 m N?m-(16),SL-n-SL的联接链为3时降低水表面张力的能力最强。吸附分子的最小截面积Amin分别是0.295 nm2、0.347 nm2和0.569 nm2,联接链越短,分子在界面层的平均占据面积越小。3.利用羧酸盐阴离子Gemini表面活性剂SL-n-SL(n=3,6,10)分别与季铵盐Gemini表面活性剂12-3(OH)-12进行复配,考察了SL-n-SL联接链长度的变化对12-3(OH)-12自组装行为的影响。研究结果表明,当联接链为3时,12-3(OH)-12溶液的粘弹性变化最明显,在阴阳离子表面活性剂摩尔比(β)为0.06时,混合溶液的零剪切粘度达到最大值(94.7 Pa·s);当联接链为6时,混合溶液在β=0.056时出现最大零剪切粘度(75 Pa·s);当联接链增加到10时,混合溶液的最大零剪切粘度基本保持不变(74.9 Pa·s)。这说明联接链的长度对复配体系胶束的形成和生长有着重要的影响。
[Abstract]:Gemini surfactant is a two parent molecule that has attracted much attention in recent years. Its novel and diversified molecular structure makes it have many unique properties of.Gemini surfactants in the head base or near the head base, which can effectively control the distance between the ionic head of the Gemini surfactant unit and make the chain density of alkanes. The charge density of the head base changed obviously. The change of the charge density of the head base was more sensitive to the action of the anti ion in the solution. In this paper, the organic salt of the isomer and the surface active agent with the opposite charge were mixed with the quaternary ammonium cationic Gemini surfactants respectively. The surface activity of Gemini was systematically studied. During the construction of the worm micelles, the small changes in the structure of the organic salt and the opposite charge surface active agent influence the formation and growth of the worm micelles and the viscoelasticity of the solution. The related results have important scientific significance for understanding the self-assembly characteristics of Gemini surfactant and summarizing the intermolecular interaction. The following contents are as follows: 1. the self-assembly of three kinds of isomers of organic salts, sodium hydroxy benzoate (o-ph-ONa), sodium hydroxy benzoate (m-ph-ONa) and sodium hydroxy benzoate (p-ph-ONa) on 2- hydroxyl Sanya methyl - alpha, Omega didodecyl three methyl bromide (12-3 (OH) -12) were studied by the steady and dynamic shear rheological experiments. Influence of the formation and growth of worm micelles in the compound system of salt /12-3 (OH) -12. The method and degree of interaction between organic salts and surfactant 12-3 (OH) -12 were verified by surface tension method and 1H-1H 2D NOESY method. The results showed that the three organic salts were all interacting with 12-3 (OH) -12 molecules and effectively promoted 12-3 (OH) -12. The formation of the molecular structure of the organic salt in the solution, the small changes in the molecular structure of the organic salts have a great influence on the formation and growth of the Gemini surfactant worm micelles, and eventually lead to the difference in the viscoelasticity of the solution. Among them, o-ph-ONa is more likely to promote 12-3 (OH) -12 molecules to form a worm micelle, m-ph-ONa, and p-ph-ONa to promote the formation of the system. A series of new carboxylate anion Gemini surfactants SL-n-SL (n=3,6,10) was synthesized by.2.. The structure of SL-n-SL (n=3,6,10) was confirmed by mass spectrometry and hydrogen spectrum. The surface activity of three carboxylate anion Gemini surface activators under 25 oC was determined by Py fluorescence probe method and surface tension method, SL-n-SL (n=3,6,10). The CMC values are 0.29mmol. L-1,0.058 mmol. L-1 and 0.012 mmol. L-1 respectively. It shows that the aggregation ability of three surfactants in aqueous solution is very strong and the strength increases with the increase of the link. The value of gamma CMC is 31.96 mN? M- (16), 36.18 mN, m- (16) and 36.27, 16), and the ability to reduce water surface tension when the link chain is 3 The minimum intercepting area Amin of the adsorbate molecule is 0.295 nm2,0.347 Nm2 and 0.569 Nm2 respectively, the shorter the link chain, the smaller the average occupying area of the molecule in the interface layer,.3. using the carboxylate anion Gemini surface active agent SL-n-SL (n=3,6,10) and the quaternary ammonium salt Gemini surfactant 12-3 (OH) -12, respectively, to investigate the length of the SL-n-SL chain length. The effect of the change on the self assembly behavior of 12-3 (OH) -12. The results show that when the link chain is 3, the viscoelastic changes of the 12-3 (OH) -12 solution are most obvious. When the mole ratio (beta) is 0.06, the zero shear viscosity of the mixed solution reaches the maximum value (94.7 Pa. S). When the link is 6, the mixed solution appears most in beta =0.056. The large zero shear viscosity (75 Pa. S), when the link increase to 10, the maximum zero shear viscosity of the mixed solution remains unchanged (74.9 Pa. S). This indicates that the length of the link chain has an important effect on the formation and growth of the micelle of the compound system.
【学位授予单位】：江南大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O647.2

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