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

采用阳离子或自由基控制聚合的方法合成了具有一条或两条明确支链的新型C&lt；60&gt；衍生物(S)。主要结果包括：1.首次将CH_3CH(O_1Bu)C_1/ZNi_2活性阳离子聚合得到的VE低聚体与VES进行活性阳离子聚合，合成了含乙烯基醚(YE)低聚物的双取代1，2-二氢[60]富勒烯。将这些C&lt；60&gt；衍生物与聚VE或聚苯乙烯(C&lt；60&>含量，5wt%)共混制得均匀透明的薄膜。合成了含有一种亲水性VE齐聚物的水溶性C_60&gt；衍生物，与已知的C_&lt；60&gt；衍生物[最大水溶解度，25.9 mg/mL(C_&lt；60&gt；部分)]相比，具有优异的水溶解性能。应用含氮自由基聚合技术首次成功合成了60-(PS-PVP)_2，其中PS为聚苯乙烯，PVP为聚对乙烯基苯酚，PS-PVP为该序列的两嵌段共聚物。研究了这些具有两个明确高分子臂的C&lt；60&gt；衍生物在某些有机溶剂中的溶解行为，如多分子胶束的形成。研究发现，胶束化伴随着UV-Vis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.