Functionalization of Carbonaceous Mesophase Spherules

本研究的目的是开发以碳颗粒为基础的功能材料。通过对碳质中间相球(球)和炭黑(CB)的表面改性，得到了以下结果：1.引入官能团对球进行表面改性(1)氧化引入酸性官能团后的样品用RSiCl3进行硅烷化反应，原始球和氧化后的球分别是疏水和亲水的。与RSiCl3反应后，它们又变得疏水，这表明在球体表面引入了RSI基团。另一方面，CB在与RSiCl3反应后仍然保持亲水性。因此，CB中引入的RSI基团很少。(2)用强碱(n-BuLi/t-BuOK)与…进行烷基化反应更多的直链芳香氢，然后与烷基碘发生烷基化反应。通过H/C比的变化估计，尽管CB比球体具有更高的比表面积，但引入到球体中的烷基数量比引入CB的要多得多。烷基化球在甲苯中分散时间较长，可用于导电涂料。通过界面反应(1)Pd(NH_3)_4~(2+)和Gt~(2+)对氧化球进行表面改性，然后在含有NiSO_4和Na_2H_2PO_2的碱性水溶液中化学镀镍，产物完全被Ni薄膜覆盖，其磁矩高达镍的一半到块体的一半。(2)氧化球在水溶液中用Na_2OnSiO_2逐步处理，在苯中和水溶液中与(NH_4)_2SO_4形成W/O的界面乳液反应。反应后，球体表面覆盖了一层二氧化硅薄膜。二氧化硅薄膜是多孔的，有可能作为催化剂用于载体。较少

The purpose of the research was to develop functional materials based on carbon particles. Following results are obtained by surface modification of carbonaceous mesophase spherules (spherules) as well as carbon blacks (CB), which expose aromatic edges and hexagonal planes to the surface, respectively :1. Surface modification of spherules by the introduction of functional groups(1) Samples after introduction of acidic functional groups by oxidation were subjected to silylation reaction by using RSiCl_3. Original spherules and ones after oxidation were hydrophobic and hydrophilic, respectively. They turned to hydrophobic again after the reaction with RSiCl_3, suggesting introduction of RSi group to the spherule surface. Number of RSi groups introduced estimated by TGA was 10^<18>/m^2. On the other hand, CB sustained hydrophilic even after the reaction with RSiCl_3. Thus, few RSi groups are introduced to CB.(2) Alkylation reaction was carried out by using strong base (n-BuLi/t-BuOK) to a … More bstract aromatic hydrogen followed by alkylation with alkyl iodides. Numbers of alkyl groups introduced to spherules estimated by the change in H/C ratios were much higher than that introduced to CB,although CB had high specific surface area than spherules. Alkylated spherules dispersed in toluene for a long period and may by applicable to conductive paints.2. Surface modification of spherules by the interfacial reactions(1) Pd (NH_3)_4^<2+> was supported on the oxidative spherules followed by electroless Ni plating in basic aqueous solutions containing NiSO_4 and Na_2H_2PO_2. The product was covered with Ni thin film completely and its magnetic moment was as high as half to bulk Ni.(2) The oxidation spherules were treated in stepwise with Na_2OnSiO_2 in aqueous solution, in benzene, and with (NH_4)_2SO_4 in aqueous solution to proceed interfacial reaction by the formation of W/O emulsion. After the reaction, spherules were covered with silica thin film. The silica film was porous and potentially applicable to a support as a catalyst. Less