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

C_<60>封端低聚物的可控聚合合成及其应用

• 批准号: 09650979
• 负责人: MIYAMOTO Takeaki
• 金额: $ 2.5万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09650979/
• 关键词: C_<60> end-capped polymers; living cationic polymerization; narrow-MWD vinyl ether oligomers; C_<60>-1,2 adduct; water-soluble C_<60> derivatives; "living" radical polymerization; narrow-MWD polystyrene; C_<60>-1,4 adduct; 安定ニトロキシル; リビングラジカル重合

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.

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聚合物臂的新型C_ 60 衍生物。主要结果包括： 1．通过将VEs的CH_3CH(O1Bu)Cl/ZnI_2进行活性阳离子聚合获得的基于VE低聚物的碳亲电子试剂添加到VEs中，首次成功合成了具有明确乙烯基醚(YE)低聚物的二取代1,2-二氢[60]富勒烯。 单辛炔基富勒阴离子。2．制备这些C_ 60 衍生物与聚VE或聚苯乙烯(C_ 60 部分，5重量％)的共混物的均匀且透明的膜。制备了具有一种亲水性VE低聚物的水溶性C_<60>衍生物，发现与迄今为止已知的C_<60>衍生物相比，具有优异的水溶性[最大水溶性，25.9mg/mL(C_<60>部分)]。 3.1，4-二取代、低多分散性C_<60>衍生物类型 利用氮氧控制的自由基首次成功合成了C_<60>-(PS)_2、C_<60>-(PVP)_2和C_<60>-(PS-PVP)_2，其中PS是聚苯乙烯，PVP是聚对乙烯基苯酚，PS-PVP是该序列的二嵌段共聚物 聚合技术.4.研究了这些具有两个明确聚合物臂的C_ 60 衍生物的溶解度行为，例如在一些有机溶剂中的多分子胶束的形成。研究发现，胶束化伴随着紫外-可见光谱的特征变化，具体取决于胶束尺寸。

项目成果

H.Okamura, T.Miyamoto et.al: "Synthesis of C_<60>-capped vinyl ether oligomers by living cationic polymerization technique" Macromol. Chem.Phys.198. 777-786 (1997)

H.Okamura、T.Miyamoto等人：“通过活性阳离子聚合技术合成C_ 60 -封端的乙烯基醚低聚物”Macromol。

H.Okamura, M,Minoda, K.Komatsu, and T.Miyamoto: ""Synthesis of C_<60>-capped vinyl ether oligomers by living cationic polymerization technique"" Macromol. Chem. Phys.198. 777-786 (1997)

H.Okamura、M、Minoda、K.Komatsu 和 T.Miyamoto：“通过活性阳离子聚合技术合成 C_ 60 -封端乙烯基醚低聚物”Macromol。

H.Okamura: "Solubility characteristics of C_<60> fullerenes with two well-defined polystyrene arms in a polystyrene matrix" Macromol.Rapid.Commun.20-2. 37-40 (1999)

H.Okamura：“聚苯乙烯基质中具有两个明确聚苯乙烯臂的 C_<60> 富勒烯的溶解度特性”Macromol.Rapid.Commun.20-2。

H.Okamura, M.Minoda et.al: "Synthesis of 1, 4-dipolystyryldihydro[60]fullerenes by using 2, 2, 6, 6-tetramethyl-1-polystyroxypiperidine as a radical source" Macromolecules. 30. 5279-5284 (1997)

H.Okamura、M.Minoda 等人：“使用 2,2,6,6-四甲基-1-聚苯乙烯氧基哌啶作为自由基源合成 1,4-二聚苯乙烯基二氢[60]富勒烯”大分子。

H.Okamura, T.Terauchi, M,Minoda, T.Fukuda, and K.Komatsu: ""Synthesis of 1,4-dipolystyryldihydro [60] fullerenes by using 2,2,6,6-tetramethyl-1-polystyroxypiperidine as a radical source"" Macromolecules. 30. 5279-5284 (1997)

H.Okamura、T.Terauchi、M、Minoda、T.Fukuda 和 K.Komatsu：“使用 2,2,6,6-四甲基-1-聚苯乙烯氧基哌啶作为 1,4-二聚苯乙烯基二氢 [60] 富勒烯的合成”