High Anionic Polymerizability of Benzofulvene: New Exo-Methylene Hydrocarbon Monomer
High Anionic Polymerizability of Benzofulvene: New Exo-Methylene Hydrocarbon Monomer
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DOI：
10.1021/acs.macromol.5b00944
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发表时间：
2015-06
期刊：
影响因子：
5.5
通讯作者：
Yuki Kosaka;S. Kawauchi;Raita Goseki;Takashi Ishizone
中科院分区：
文献类型：
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作者：
Yuki Kosaka;S. Kawauchi;Raita Goseki;Takashi Ishizone
在-78℃下，在THF中，用仲丁基锂、二苯基甲基锂、二苯基甲基钾、三苯基甲基锂和三苯基甲基钾等各种引发剂定量地进行苯并富烯（BF）的阴离子聚合，得到具有基于摩尔比预测分子量的聚合物。 BF 和引发剂且分子量分布窄（MWD，Mw/Mn < 1.1）。虽然引发效率无法定量，但BF也可以与氯化苄镁、叔丁醇钾和阴离子活性聚甲基丙烯酸叔丁酯聚合，表明BF具有较高的阴离子聚合能力。通过密度泛函理论 (DFT) 计算得到的 BF 的平面构象和极化电子密度支持观察到的阴离子聚合性高于 BF 的无环类似物 2-苯基-1,3-丁二烯。一系列新型嵌段共聚物，聚苯乙烯-b-聚(BF)、聚(2-乙烯基吡啶)-b-聚(BF)、聚(甲基丙烯酸叔丁酯)...
The anionic polymerization of benzofulvene (BF) quantitatively proceeded with various initiators, such as sec-BuLi, diphenylmethyllithium, diphenylmethylpotassium, triphenylmethyllithium, and triphenylmethylpotassium, in THF at −78 °C to give polymers having predicted molecular weights based on the molar ratios between BF and the initiators and narrow molecular weight distributions (MWD, Mw/Mn < 1.1). Although the initiation efficiencies were not quantitative, BF could also be polymerized with benzylmagnesium chloride, potassium tert-butoxide, and the anionic living poly(tert-butyl methacrylate), indicating the high anionic polymerizability. The planar conformation and the polarized electron density of BF obtained by the density functional theory (DFT) calculation supported the observed anionic polymerizability higher than that of 2-phenyl-1,3-butadiene, the acyclic analogue of BF. A series of new block copolymers, polystyrene-b-poly(BF), poly(2-vinylpyridine)-b-poly(BF), and poly(tert-butyl methacrylate)...