Anionic Polymerization of 2-Hexyl[3]dendralene
Anionic Polymerization of 2-Hexyl[3]dendralene
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DOI：
10.1002/macp.201700046
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发表时间：
2018-01-05
影响因子：
2.5
通讯作者：
Shiomi, Tomoo
中科院分区：
文献类型：
--
作者：
Takamura, Yuki;Takenaka, Katsuhiko;Shiomi, Tomoo
本研究考察了烷基基衍生[3]树突烯2-己基[3]树突烯（H3D）的聚合行为。H3D在四氢呋喃（THF）中以萘化钾为引发剂，在-78℃下聚合得到分子量分布窄的聚（H3D），尽管在单体完全消耗之前，在高分子量时观察到一个小肩峰。在庚烷中制备的聚（H3D）的分子量分布比在THF中制备的更宽，这表明除了聚合之外，在聚合物链的碳-碳双键上还发生了增殖碳离子的亲核加成。此外，通过核磁共振对聚H3D的微观结构进行了研究。对应于共轭加成结构即1,4-和4,6-结构的信号被独占地观察到。在庚烷中制备的聚（H3D）比在四氢呋喃中制备的聚（H3D）含有更高的4,6结构。
In this study, the polymerization behavior of 2-hexyl[3]dendralene (H3D), which is an alkyl-group-derived [3]dendralene, is examined. The polymerization of H3D in tetrahydrofuran (THF) at -78 degrees C with potassium naphthalenide as the initiator affords poly(H3D) with a narrow molecular weight distribution, although a small shoulder peak is observed at a high molecular weight even before the monomer is completely consumed. The molecular weight distribution of poly(H3D) prepared in heptane is broader than that prepared in THF, indicating that the nucleophilic addition of a propagating carbanion to the carbon-carbon double bond in the polymer chain occurs in addition to polymerization. Furthermore, the microstructure of poly(H3D) is investigated by NMR. Signals corresponding to the conjugate addition structure, that is, 1,4- and 4,6-structures, are exclusively observed. Poly(H3D) prepared in heptane contains a higher content of the 4,6-structures compared with those prepared in THF.