Synthesis of C_<60> end-capped oligomers by controlled polymerization and their applications

通过阳离子或自由基控制聚合，合成了具有一个或两个明确的聚合物臂的新型C_<60>衍生物。主要结果包括：1。采用CH_3CH(O1Bu)C1/ zni_2催化活性阳离子聚合得到VE低聚物为基础的碳亲电试剂，在单辛酰基富勒烯阴离子上加入VE，首次成功合成了具有良好定义的乙烯醚（YE）低聚物的1,2-二氢[60]富勒烯。这些C_<60>衍生物与聚苯乙烯（C_<60>部分，5 wt%）共混制备了均匀透明的薄膜。制备了含1个亲水性VE低聚物的水溶性C_<60>衍生物，与目前已知的C_<60>衍生物（最大水溶性25.9 mg/mL （C_<60>部分））相比，具有良好的水溶性。3.1,4-二取代，低多分散性C_<60 b>衍生物C_<60>-(PS)_2, C_<60>-(PVP)_2和C_<60>-(PS-PVP)_2，其中PS为聚苯乙烯，PVP为聚对乙烯基酚，PS-PVP为该序列的双嵌段共聚物。采用氮氧自由基控制聚合技术，首次成功合成了三种不同类型的化合物。研究了这些C_<60>衍生物在有机溶剂中的溶解度行为，如多分子胶束的形成。研究发现，胶束化过程伴随着紫外可见光谱的特征变化，这取决于胶束的大小。

New types of C_<60> derivatives with one or two well-defined polymer arm(s) were synthesized by the cationic or radical controlled polymerization. Main results include :1. Disubstituted 1,2-dihydro[60]fullerenes having a well-defined vinyl ether (YE) oligomer were successfully synthesized for the first time by the addition of the VE oligomer-based carbon electrophile, which was obtained by the CH_3CH(O1Bu)C1/ZnI_2-conducted living cationic polymerization of VEs, to the mono-octynylfulleride anion.2. Homogeneous and transparent films of the blends of these C_<60> derivatives with polyVE or polystyrene (C_<60> moiety, 5 wt%) were prepared. The water-soluble C_<60> derivative with one hydrophilic VE oligomer was prepared, and found to have excellent aqueous solubility compared to the C_<60> derivatives thus far known [the maximum aqueous solubility, 25.9 mg/mL (C_<60> moiety)].3.1,4-Disubstituted, low-polydispersity C_<60> derivatives of types C_<60>-(PS)_2, C_<60>-(PVP)_2, and C_<60>-(PS-PVP)_2, where PS is polystyrene, PVP is poly(p-vinylphenol), and PS-PVP is a diblock copolymer of this sequence, were successfully synthesized for the first time by applying the nitroxide-controlled free radical polymerization technique.4. These C_<60> derivatives with two well-defined polymer arms were studied with their solubility behaviors such as the multimolecular micelles formation in some organic solvents. It was found that the micellization is accompanied by characteristic changes in the UV-vis spectra, depending on micelle size.