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Formation and structure of organized molecular films for fluorinated comb copolymers

机译：含氟梳状共聚物的有序分子膜的形成与结构

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摘要

The molecular orientation in monolayer and multilayer films of fluorinated comb copolymers with various monomer ratios can be characterized by in-plane and out-of plane X-ray diffraction (XRD), near-edge X-ray absorption fine structures (NEXAFS) spectroscopy at the C K-edges, and atomic force microscopic observation. And further, the fine structure in the solid state and phase transition behavior of newly synthesized comb copolymers having fluorocarbon and hydrocarbon side-chains were investigated by temperature controlled wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). From the WAXD profiles, two kinds of short spacing peaks based on the formation of the sub-cell for fluorinated and hydrogenated side-chains were confirmed at 5.0 and 4.1A, respectively. Furthermore, two kinds of endothermic peaks, which corresponded to melting peaks of both side-chain crystals, appeared in the heating process of the DSC thermograms. From these experimental findings, the phase separation structure having the independently packed immiscible side-chain crystalline formed in the whole polymer crystal. In addition, it was found that these comb polymers formed highly ordered (double) layer structures estimated using WAXD and small-angle X-ray scattering (SAXS). These fluorinated comb copolymers form the monolayer on the water surface and their transferred film with phase separated structure at nanometer size on the solid. There were hydrogenated domains at 10-20nm diameter scales in these phase separated surface structures of the monolayers. From these experimental results, these copolymer monolayers are expected to be used as in new molecular devices such as nano-lithography based on the surface patterning of polymer nano-materials.
机译：具有不同单体比例的氟化梳形共聚物的单层和多层膜中的分子取向可以通过在60℃下进行面内和面外X射线衍射（XRD），近边缘X射线吸收精细结构（NEXAFS）光谱表征C K边缘和原子力显微镜观察。而且，通过温度控制的广角X射线衍射（WAXD）和差示扫描量热法（DSC）研究了具有碳氟化合物和烃侧链的新合成的梳型共聚物的固态细相结构和相变行为。根据WAXD曲线，分别在5.0和4.1A处确定了两种基于氟化和氢化侧链子电池形成的短间距峰。此外，在DSC温谱图的加热过程中出现了两种吸热峰，它们对应于两个侧链晶体的熔融峰。从这些实验发现，相分离结构具有在整个聚合物晶体中形成的独立包装的不混溶的侧链晶体。另外，发现这些梳状聚合物形成使用WAXD和小角度X射线散射（SAXS）估计的高度有序的（双层）结构。这些氟化梳状共聚物在水表面上形成单层，并在固体表面上形成具有纳米尺寸相分离结构的转移膜。在单层的这些相分离的表面结构中，存在直径为10-20nm的氢化区域。从这些实验结果来看，这些共聚物单层有望用于新的分子装置中，例如基于聚合物纳米材料表面图案的纳米光刻。

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