物理化学学报 >> 2010, Vol. 26 >> Issue (02): 324-330.doi: 10.3866/PKU.WHXB20100204

胶体及界面化学 上一篇    下一篇

两亲无规聚合物的聚集行为及其与非离子表面活性剂的相互作用

吴旭, 乔英杰, 胡长朝, 杨惠, 王金本   

  1. 哈尔滨工程大学材料科学与化学工程学院, 哈尔滨 150001; 中国科学院化学研究所, 胶体、界面与化学热力学院重点实验室, 北京 100190
  • 收稿日期:2009-10-12 修回日期:2009-11-17 发布日期:2010-01-26
  • 通讯作者: 王金本 E-mail:jbwang@iccas.ac.cn

Aggregation Behavior of Amphiphilic Statistical Polymers and Their Interactions with Nonionic Surfactants

WU Xu, QIAO Ying-Jie, HU Chang-Chao, YANG Hui, WANG Jin-Ben   

  1. College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, P. R. China; Key Laboratory of Colloid, Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China
  • Received:2009-10-12 Revised:2009-11-17 Published:2010-01-26
  • Contact: WANG Jin-Ben E-mail:jbwang@iccas.ac.cn

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摘要：

以2-丙烯酰胺基-十二烷基磺酸(AMC12S)与2-丙烯酰胺基-2-甲基丙磺酸(AMPS)进行无规共聚, 合成了含AMC12S摩尔分数(X)较高(X=0.1, 0.3, 0.5)的一系列两亲聚合物. 采用稳态荧光及动态光散射技术对聚合物在水溶液中的聚集行为及其与三种非离子表面活性剂(HO(CH2CH2O)10C12H25 (C12E10)、HO(CH2CH2O)20C12H25 (C12E20)和HO(CH2CH2O)40C12H25(C12E40))的相互作用进行了研究, 并考察了X对聚集行为的影响以及表面活性剂亲水基团长度对相互作用的影响. 随着X的增大, 聚合物的临界聚集浓度(CAC)明显减小, X=0.5时聚合物的CAC低达0.0039 g·L-1. 聚集体的流体力学半径(Rh)都大于26 nm, 并随着聚合物浓度的升高而增大, 说明聚合物分子主要以分子间的聚集方式聚集, 形成多分子聚集体. 随X的增大, 聚集体Rh减小, 同时Rh随聚合物浓度升高而增大的幅度减小, 说明聚集体结构变得更加紧实. 表面活性剂与聚合物之间存在很强的相互作用, 在混合溶液中表面活性剂浓度达到临界胶束浓度(CMC)左右时聚合物聚集体开始解离, 形成混合聚集体. 亲水基团长度增长, 表面活性剂对聚合物聚集体的解离能力随之增强. C12E40与X=0.5的聚合物形成的混合聚集体Rh为6.8 nm, 与C12E40自身形成的聚集体尺寸相当.

关键词: 非离子表面活性剂, 两亲聚合物, 聚集行为, 聚集体, 相互作用

Abstract:

A series of amphiphilic polymers were synthesized by the statistical polymerization of 2-(acrylamido)-dodecanesulfonic acid (AMC12S) with 2-(acrylamido)-2-methylpropanesulfonic acid (AMPS) and they contained a high mole fraction of AMC12S (X=0.1, 0.3, 0.5). The aggregation behaviors of the polymers and their interactions with three nonionic surfactants HO(CH2CH2O)10C12H25 (C12E10), HO(CH2CH2O)20C12H25 (C12E20), and HO(CH2CH2O)40C12H25 (C12E40) in aqueous solutions were investigated by steady-state fluorescence and quasi-elastic light scattering measurements. The effect of X on the association performance and the influence of the surfactant's hydrophilic group length on these interactionswere also investigated. The critical aggregationconcentration(CAC) of the polymerwas found to significantly decrease with increasing X. The CAC of the polymer with X=0.5 is as low as 0.0039 g·L-1. The hydrodynamic sizes of the aggregates (Rh) are larger than 26 nm and increase with an increase in polymer concentration, indicating that the polymeric molecules exhibit a strong tendency for interpolymer association, leading to the formation of multimolecular aggregates. When X increases, both Rh and its tendency to increase decrease, suggesting that the aggregates become more compact. The interaction between surfactant and polymer is very strong and the polymer aggregates begin to collapse when the surfactant concentration reaches the critical micelle concentration (CMC) in the mixed solutions and mixed aggregates form. The destructive ability of the surfactant increases as the length of the hydrophilic group increases. The Rh value of the mixed aggregates formed by C12E40 and the polymer with X=0.5 is 6.8 nm, which is consistent with the Rh value of the C12E40 aggregates.

Key words: Nonionic surfactant, Amphiphilic polymer, Aggregation behavior, Aggregate, Interaction