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Investigation of the interactions of cationic polyelectrolytes with anionic surfactants: Effects of polymer, surfactant and solution properties.

机译：阳离子聚电解质与阴离子表面活性剂相互作用的研究：聚合物，表面活性剂和溶液性质的影响。

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摘要

The intent of this research is to explore and understand the effects that a range of polymer, surfactant and solution parameters have on the interaction of oppositely-charged polymers and surfactants. Cationic polysaccharides were chosen for this research because they are known to interact with anionic surfactants, and they offer a wide range of adjustable polymer properties, including molecular weight, charge substitution, and backbone structure. Cationic poly(vinylpyridinium hydrochloride) polymers were chosen for these studies because they provide the opportunity to explore the effects of charge position on the interaction of cationic polymers with anionic surfactants and how this influences the mechanism of interaction. The overall goal of this research is to define the effects of polymer and surfactant structural properties, and solution properties, on the interaction between cationic polymers and anionic surfactants, and the subsequent formation of coacervate in these systems.;The interaction of cationic polymers with varying properties with anionic surfactant was studied using conventional microscopic and macroscopic methodologies to probe the mechanism of interaction in these systems. Polyquaternium-10 systems interacted with anionic surfactant in accordance with the cooperative mechanism of interaction and coacervate formation as described by Goddard. The mechanism of interaction between poly(vinylpyridinium hydrochloride) polymers and anionic surfactant was found to be dependent on the position of the cationic charge relative to the hydrophobic polymer backbone. Polymer-surfactant interaction with poly(4vinylpyridinium hydrochloride) and anionic surfactant occurred via the site-specific cooperative mechanism of interaction. However, the interaction of poly(2-vinylpyridinium hydrochloride) with anionic surfactant exhibited characteristics of the site-specific cooperative interaction mechanism as well as the macroion-macroion interaction mechanism.;A high-throughput screening method was developed to facilitate systematic studies of the effects of polymer, surfactant and solution properties on the macroscopic property of coacervate formation. This method allowed rapid and reproducible preparation and analysis of multi-component systems and representation of the amount of coacervate and compositional range of coacervate formation in these systems in easily understood contour phase diagrams. In the cationic polysaccharide systems, the amount of coacervate and the compositional range of coacervate formation displayed a dependence on both the polymer charge density and molecular weight. Also, the polymer critical overlap concentration was observed to affect coacervate amount with higher coacervate formation observed above c*.;Coacervate formation with the poly(vinylpyridinium hydrochloride) polymers was found to be dependent not only on the position of the cationic charge on the polymer, but also on the structure of the surfactant tail group. Coacervate formed initially with P4VP and P2VP and sodium capryl sulfonate and sodium xylene sulfonate was not stable over 24 hours, however coacervate formed between these polymers and sodium dodecylbenzene sulfonate was stable over 24 hours. This indicates that a hydrophobic chain with sufficient length and/or an aromatic group is necessary to form thermodynamically stable coacervate.;The effect of salt in solution on polymer-surfactant interaction was studied with both classes of polymer. A dependence of coacervate amount and compositional range of coacervate formation on salt concentration was observed. The effect of salt was dependent on the degree of polymer charge substitution. The order of addition of polymer, surfactant, and salt also affected coacervate formation. This was consistent for both low and high molecular weight polymers, as well as low and high charge substituted polymers. Although an effect of addition order was observed in all systems, the specific effects differed depending on the polymer properties.
机译：这项研究的目的是探索和理解一系列聚合物，表面活性剂和溶液参数对带相反电荷的聚合物和表面活性剂相互作用的影响。选择阳离子多糖进行这项研究是因为已知它们与阴离子表面活性剂相互作用，并且它们提供了广泛的可调节聚合物特性，包括分子量，电荷取代和主链结构。选择阳离子聚（乙烯基吡啶鎓盐酸盐）聚合物进行这些研究是因为它们提供了探索电荷位置对阳离子聚合物与阴离子表面活性剂相互作用的影响以及这如何影响相互作用机理的机会。这项研究的总体目标是确定聚合物和表面活性剂的结构性质以及溶液性质对阳离子聚合物和阴离子表面活性剂之间的相互作用以及随后在这些体系中形成凝聚层的影响。使用常规的微观和宏观方法研究了阴离子表面活性剂的化学性质，以探讨这些系统中相互作用的机理。按照Goddard所述，Polyquaternium-10系统与相互作用和凝聚层形成的协同机理与阴离子表面活性剂相互作用。发现聚（乙烯基吡啶鎓盐酸盐）聚合物与阴离子表面活性剂之间的相互作用机理取决于阳离子电荷相对于疏水聚合物主链的位置。聚合物-表面活性剂与聚（4-乙烯基吡啶盐酸盐）和阴离子表面活性剂的相互作用是通过特定位置的相互作用相互作用发生的。然而，聚（2-乙烯基吡啶鎓盐酸盐）与阴离子表面活性剂的相互作用表现出了位点特异性的相互作用机理以及宏观离子-大分子离子相互作用机理的特征。 ，表面活性剂和溶液性质对凝聚层形成宏观性质的影响这种方法可以快速，可重现地制备和分析多组分系统，并以易于理解的轮廓相图表示这些系统中凝聚层的数量和凝聚层的组成范围。在阳离子多糖体系中，凝聚层的量和凝聚层形成的组成范围显示出对聚合物电荷密度和分子量的依赖。同样，观察到聚合物临界重叠浓度会影响凝聚层的数量，并在c *以上观察到更高的凝聚层形成；发现聚（乙烯基吡啶鎓盐酸盐）聚合物的凝聚层形成不仅取决于聚合物上阳离子电荷的位置，而且在表面活性剂尾基的结构上。最初与P4VP和P2VP形成的凝聚层，辛酸磺酸钠和二甲苯磺酸钠在24小时内不稳定，但是这些聚合物与十二烷基苯磺酸钠之间形成的凝聚层在24小时内稳定。这表明具有足够长度和/或芳族基团的疏水链对于形成热力学稳定的凝聚层是必需的。两种类型的聚合物都研究了溶液中盐对聚合物-表面活性剂相互作用的影响。观察到凝聚层的量和凝聚层形成的组成范围对盐浓度的依赖性。盐的作用取决于聚合物电荷取代的程度。聚合物，表面活性剂和盐的添加顺序也影响凝聚层的形成。这对于低分子量和高分子量聚合物以及低电荷和高电荷取代的聚合物都是一致的。尽管在所有体系中均观察到添加顺序的影响，但是具体效果取决于聚合物性能而不同。

著录项

  • 作者

    Huisinga, Lisa Renee.;

  • 作者单位

    The University of Southern Mississippi.;

  • 授予单位 The University of Southern Mississippi.;
  • 学科 Chemistry Polymer.
  • 学位 Ph.D.
  • 年度 2008
  • 页码 221 p.
  • 总页数 221
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 高分子化学（高聚物）;
  • 关键词

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