Anionic Polymerization of 2-Phenyl[3]dendralene and 2-(4-Methoxyphenyl)[3]dendralene

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• 作者：Katsuhiko Takenaka ; Shuhei Amamoto ; Hiroto Kishi ; Hiroki Takeshita ; Masamitsu Miya ; Tomoo Shiomi
• 刊名：Macromolecules
• 出版年：2013
• 出版时间：September 24, 2013
• 年：2013
• 卷：46
• 期：18
• 页码：7282-7289
• 全文大小：399K
• 年卷期：v.46,no.18(September 24, 2013)
• ISSN：1520-5835

文摘

Anionic polymerization of two phenyl-substituted trienes containing cross-conjugated carbon鈥揷arbon double bonds, 2-phenyl[3]dendralene (P3D) and 2-(4-methoxyphenyl)[3]dendralene (MP3D), was carried out in THF under a variety of different conditions. Poly(P3D) of controlled molecular weight with a narrow molecular weight distribution was obtained when the polymerization reaction was carried out at 鈭?8 掳C for 30 min. Broadening of the molecular weight distribution to the higher-molecular-weight side was observed if the polymerization mixture was left to stand for 20 h at 鈭?8 掳C, presumably because of the attack of the propagating chain-end carbanion at the conjugated diene structure in the polymer chain. Similar broadening occurred if the polymerization was performed at a higher temperature. However, under identical conditions, no such a broadening was observed in the polymerization of MP3D. Block copolymers of predictable molecular weights and compositions containing a poly(2-vinylpyridine) segment were obtained by the sequential addition of P3D and/or MP3D to potassium naphthalenide and then 2-vinylpyridine. Only the conjugate addition structure was found in the resulting polymers.