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

通过<60>阳离子或自由基控制聚合，合成了一类具有一个或两个明确聚合物臂的新型C_2衍生物。主要结果包括：1.通过CH_3CH（O 1Bu）Cl/ZnI_2催化乙烯基醚（VE）的活性阳离子聚合得到的VE低聚物碳亲电试剂与单辛炔基富勒烯阴离子的加成反应，首次成功合成了具有明确结构的乙烯基醚（YE）低聚物的二取代1，2-二氢[60]富勒烯.制备了这些C_<60>衍生物与聚乙烯或聚苯乙烯（C_<60>部分，5wt%）的共混物的均匀透明膜。制备<60>了含有一个亲水性VE低聚物的水溶性C_衍生物，并发现其具有优异的水溶性<60>[最大水溶解度为25.9 mg/mL（C_<60>moiety）]。3.首次采用氮氧自由基聚合技术成功合成<60>了C_<60>-（PS）_2、C_<60>-（PVP）_2和C_<60>-（PS-PVP）_2型1，4-二取代、低多分散性C_衍生物，其中PS为聚苯乙烯，PVP为聚对乙烯基苯酚，PS-PVP为该序列的二嵌段共聚物。研究了这类<60>具有两个明确聚合物臂的C_2衍生物在有机溶剂中的溶解行为，如形成多分子胶束的行为。结果发现，胶束化伴随着特征的变化，在紫外-可见光谱，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.