Functionalization of Carbonaceous Mesophase Spherules

这项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粒（spherules）和炭黑（CB）进行表面改性，分别使芳香边和六边形面暴露在表面，得到了以下结果：(1)氧化引入酸性官能团后的样品用RSiCl_3进行硅基化反应。原始球粒和氧化后球粒分别为疏水性和亲水性。与RSiCl_3反应后，它们再次变为疏水性，表明RSi基团被引入到球粒表面。TGA估计引入的RSi基团数为10^<18>/m^2。另一方面，与RSiCl_3反应后，CB仍保持亲水性。因此，很少有RSi组被引入到CB。(2)采用强碱（n-BuLi/t-BuOK）与芳香族氢进行烷基化反应，再与碘化烷基进行烷基化反应。通过H/C比值的变化估计引入到球体中的烷基数量远高于引入到CB的烷基数量，尽管CB比球体具有更高的比表面积。烷基化小球在甲苯中长期分散，可用于导电涂料。(1)在含NiSO_4和Na_2H_2PO_2的碱性水溶液中，将Pd (NH_3)_4^<2+>支撑在氧化球上，然后进行化学镀镍。该产品被镍薄膜完全覆盖，其磁矩高达体镍的一半。(2)用Na_2OnSiO_2水溶液、苯溶液和（NH_4）_2SO_4水溶液对氧化球进行分步处理，形成W/O乳液。反应结束后，小球体被二氧化硅薄膜覆盖。二氧化硅薄膜是多孔的，可能适用于作为催化剂的载体。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