Living anionic polymerizations of 4-(1-adamantyl)styrene and 3-(4-vinylphenyl)-1,1'-biadamantane
Living anionic polymerizations of 4-(1-adamantyl)styrene and 3-(4-vinylphenyl)-1,1'-biadamantane
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DOI：
10.1021/ma060977
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发表时间：
2006-08
期刊：
影响因子：
5.5
通讯作者：
Shingo Kobayashi;T. Matsuzawa;S. Matsuoka;H. Tajima;Takashi Ishizone
中科院分区：
文献类型：
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作者：
Shingo Kobayashi;T. Matsuzawa;S. Matsuoka;H. Tajima;Takashi Ishizone
新苯乙烯衍生物 4-(1-金刚烷基)苯乙烯 (1) 和 3-(4-乙烯基苯基)-1,1'-联金刚烷 (2) 与仲丁基锂、异丙苯钾和萘化锂或萘化钾在 THF 中于 -78 °C 下进行阴离子聚合 3−4 小时。 1和2的聚合反应定量进行，得到的聚合物具有基于单体和引发剂之间的摩尔比的预测分子量以及窄分子量分布（Mw/Mn = 1.03−1.13）。通过1和2与苯乙烯或异戊二烯顺序共聚的定量引发效率证实了聚(1)和聚(2)增长链端的稳定性。阴离子合成了新型明确的嵌段共聚物：聚(1)-b-聚苯乙烯、聚(1)-b-聚异戊二烯、聚(1)-b-聚异戊二烯-b-聚(1)、聚(2)-b-聚苯乙烯和聚(2)-b-聚异戊二烯-b-聚(2)。所得聚 (1) 和聚 (2) 在超过 340 °C 时开始分解，并表现出非常高的玻璃化转变温度（...
Anionic polymerizations of new styrene derivatives, 4-(1-adamantyl)styrene (1) and 3-(4-vinylphenyl)-1,1‘-biadamantane (2), were carried out with sec-butyllithium, cumylpotassium, and lithium- or potassium naphthalenide in THF at −78 °C for 3−4 h. The polymerizations of 1 and 2 quantitatively proceeded to afford the polymers possessing the predicted molecular weights based on the molar ratios between monomers and initiators and the narrow molecular weight distributions (Mw/Mn = 1.03−1.13). The stability of propagating chain ends of poly(1) and poly(2) was confirmed by the quantitative initiation efficiency in the sequential copolymerization of 1 and 2 with styrene or isoprene. Novel well-defined block copolymers, poly(1)-b-polystyrene, poly(1)-b-polyisoprene, poly(1)-b-polyisoprene-b-poly(1), poly(2)-b-polystyrene, and poly(2)-b-polyisoprene-b-poly(2), were anionically synthesized. The resulting poly(1) and poly(2) started to decompose over 340 °C and showed remarkably high glass transition temperatures (...