Theoretical Analysis of the Crosslinking Effect on the Polyelectrolyte-Surfactant Interaction
Theoretical Analysis of the Crosslinking Effect on the Polyelectrolyte-Surfactant Interaction
复制标题
交联效应对聚电解质-表面活性剂相互作用的理论分析
DOI：
10.1021/j100027a043
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发表时间：
1995
期刊：
影响因子：
--
通讯作者：
Y. Osada
中科院分区：
文献类型：
--
作者：
J. Gong;Y. Osada
表面活性剂分子与带电聚合物网络的化学计量结合的特征在于两个过程。一种是表面活性剂离子与带相反电荷的网络之间的静电相互作用，形成盐状桥接，从而引发结合。另一种是结合的表面活性剂之间的疏水相互作用，其以这样的方式稳定聚集体，使得沿着聚合物链沿着已经占据的位点的相邻部分沉降。前者被称为“启动过程”，后者被称为“合作过程”。人们对表面电荷-线性电荷相互作用进行了大量的研究。1-6 Zimm-Bragg 7理论是针对生物大分子的螺旋-卷曲转变而提出的，它很好地描述了表面活性剂与大分子的协同结合过程。1，8然而，只有少数研究已经取得了表面活性剂-聚合物网络的相互作用。9· 10 Khokhlov et al. 9提出了一个弱电荷的网络理论，该网络浸没在带相反电荷的表面活性剂溶液中。在他们的理论中，网络的溶胀和塌陷得到了很好的描述，但没有考虑网络和表面活性剂之间的静电相互作用。Tanaka等人10研究了N-异丙基丙烯酰胺（NIPA）凝胶在表面活性剂水溶液中的溶胀平衡随温度的变化，并将体积相变理论发展到表面活性剂的情况。我们对表面活性剂与带相反电荷的线性和网络聚合物的结合进行了比较研究11- 14，并发现网络的结合的起始发生在低至10-5 mol/L的表面活性剂浓度下。这比线性聚合物低1个数量级，尽管网络的传播过程被显著抑制（线性聚合物的协同性参数为630，而聚合物网络的协同性参数为~ 1）并且协同性实际上被禁止。11本文试图从理论上归因于交联对表面活性剂结合的作用和影响。疏水性相互作用的贡献已使用最初由Marcus用于聚电解质滴定的最近邻相互作用模型来处理。表15表面活性剂与线性分子以及与
The stoichiometric binding of surfactant molecules with the charged polymer network is characterized by two processes. One is the electrostatic interaction between the surfactant ion and the oppositely charged network to form salt-like bridging, thus initiating the binding. The other is the hydrophobic interaction between bound surfactants, which stabilizes the aggregation in such a way as to settle the adjacent to the already occupied site along the polymer chain. The former is called “initiation process” and the latter is called “cooperative process”. A number of researches regarding the surfactant—linear polyelectrolyte interaction have been made. 1-6 The cooperative binding process of surfactant with macromolecules has been well described by Zimm—Bragg7 theory, which was proposed for the helix-coil transition of biopolymers. 1, 8 However, only a few studies have been made on the surfactant—polymer network interaction. 9· 10 Khokhlov et al. 9 proposed a theory of weakly charged polyelectrolyte networks immersed in the solution of an oppositely charged surfactant. In their theory, the swelling and collapse of the network was well described, but the electrostatic interaction between the network and the surfactant was not taken into account. Tanaka et al. 10 studied the swelling equilibrium of/V-isopropylacrylamide (NIPA) gel as a function of temperature in aqueous solutions of surfactant and developed the volume-phase transition theoryto the case of surfactant.We have made a comparative study on the surfactant binding with oppositely charged linear and network polymers11-14 and found that the initiation of the binding of the network occurs at a surfactant concentration as low as 10-5 mol/L. Thisis 1 order of magnitude lower than that of linear polyelectrolyte, although the propagation process of the network was significantly suppressed (the cooperativity parameter for linear polymer was 630, while that of the polymer network was~ 1) and the cooperativity was practically prohibited. 11 This paper attempts to theoretically ascribe the role and effect of the cross-linkage on the surfactant binding. The contribution of the hydrophobic interaction has been treatedusing the nearest neighbor interaction model originally employed for polyelectrolyte titration by Marcus. 15 General formulas for the binding of surfactant with a linear polyelectrolyte as well as with a