Fundamental Study of Polymer Organization at the Interfaces by the Fusion of Organic Chemistry and Physical Chemistry

从合成到纳米结构分析，系统地研究了离子型两亲嵌段共聚物的分子性质和自组装行为，如在水中的胶束和在空气/水界面上的单分子层，发现离子型两亲嵌段共聚物在溶液中形成胶束，但显示出“非表面活性”。由于这种现象超出了表面和界面科学的常识，因此这种聚合物可以被视为一种新的物质。通过对不同链长和链长比的嵌段共聚物的考察，将非表面活性的原因归结为气/水界面的像电荷效应，并定量地阐明了非表面活性的要求。非表面活性是通过精确平衡聚合性、离子性和疏水性三个因素实现的。聚合物胶束在水中对盐的加成显示出极高的韧性。在高达0.5M NaCl的条件下，未形成聚集体。结构 ...更多信息 用X射线和中子反射率技术系统地研究了它们在水表面上形成的聚合物单分子层的纳米结构。单层结构不是简单的疏水和亲水刷层的双层，而是三层，它们之间有“地毯”层。地毯层是致密的亲水层，其厚度几乎恒定在15微米。可以估计双层和三层结构之间的过渡的临界刷密度。此外，临界盐浓度，其中纳米结构的变化发生的盐加成，被发现在10 μ <-1>M salt.总之，“新物质”，离子型两亲性嵌段共聚物的性能和自组装行为，可以澄清的两亲性聚合物的旋进合成和纳米结构分析与散射和反射率的高技术的融合。少

Molecular properties and self-assemblies, such as micelle in water and monolayer at the air/water interface, of ionic amphiphilic diblock copolymers were systematically investigated from synthesis to nanostructure analysis.Unexpectedly, the ionic amphiphilic block copolymers shows "non-surface activity" but forms micelles in solution. Since this phenomenon is out of commonsense of surface and interface science, this polymer can be regarded as a novel substance. By investigation with block copolymer with various chain length and length ratios, the origin of the non-surface activity could be attributed to the image charge effect at the air/water interface, and the requirements to be non-surface active were quantitatively clarified. The non-surface activity is achieved by the accurate balance of three factors, polymerity, ionicity, and hydrophobicity.The polymer micelle in water shows extremely high toughness against salt addition. No aggregates were formed up to 0.5M NaCl. The structure … More transition between spherical and rod-like micelles were also observed as a function of chain length and salt concentration.The nanostructure of their polymer monolayer on the water surface was systematically investigated by X-ray and neutron reflectivity techniques. The monolayer structure is not a simple double layer of hydrophobic and hydrophilic brush layers, but is triple layer with "carpet" layer between them. The carpet layer is dense hydrophilic layer, whose thickness is almost constant at 15Å. The critical brush density for the transition between double and triple layer structures could be estimated. Also, the critical salt concentration, where nanostructure change occurs by salt addition, was found to be in the order of 10^<-1>M salt.In conclusion, the properties and self-assembling behavior of "novel substance", ionic amphiphilic diblock copolymer, could be clarified by the fusion of high techniques for precession synthesis of amphiphilic polymers and for nanostructure analysis with scattering and reflectivity. Less