Addition Polymerization of 2-Aryl- and 2-Ethoxycarbonyl-1-methylenecyclopropanes Promoted by Nickel Complexes
Addition Polymerization of 2-Aryl- and 2-Ethoxycarbonyl-1-methylenecyclopropanes Promoted by Nickel Complexes
复制标题
镍配合物促进的 2-芳基-和 2-乙氧基羰基-1-亚甲基环丙烷的加成聚合
DOI：
10.1021/ma020988c
复制
发表时间：
2002
期刊：
影响因子：
5.5
通讯作者：
K. Osakada
中科院分区：
文献类型：
--
作者：
Daisuke Takeuchi;Kouhei Anada;K. Osakada
[Ni(π-C3H5)Br]2引发了2-芳基-1-亚甲基环丙烷和2-乙氧羰基-1-亚甲基环丙烷的加成聚合，得到了具有环丙基的聚合物。聚合物的1H和13C核磁共振谱表明单体单元的头尾连接得到了良好的调节。D2O猝灭2-苯基-1-亚甲基环丙烷的聚合，形成具有- CH2D端基的聚合物，这与单体在Ni -碳键上的1,2插入比2,1插入更一致。在- 40℃下制备的2-苯基-1-亚甲基环丙烷聚合物的GPC显示，基于聚苯乙烯标准的Mn = 29 000 （Mw/Mn = 1.59）。2-芳基-1-亚甲基环丙烷聚合物的分子量随着单体芳香族吸电子取代基的增加而增加。对2-芳基-1-亚甲基环丙烷聚合物的DSC和TG分析表明，在153 ~ 178℃的温度范围内发生玻璃化转变，在352 ~ 361℃的温度范围内由于热分解而失重5%。2-乙基…
[Ni(π-C3H5)Br]2 initiates addition polymerization of 2-aryl-1-methylenecyclopropanes and 2-ethoxycarbonyl-1-methylenecyclopropane, affording the polymers having cyclopropylidene groups. The 1H and 13C NMR spectra of the polymers indicate well-regulated head-to-tail linkage of the monomer units. Quenching of polymerization of 2-phenyl-1-methylenecyclopropane by D2O forms the polymer with −CH2D terminal group, which is more consistent with 1,2-insertion of the monomer to the Ni−carbon bond than 2,1-insertion. GPC of the polymer of 2-phenyl-1-methylenecyclopropane prepared at −40 °C shows Mn = 29 000 (Mw/Mn = 1.59) based on polystyrene standards. Molecular weight of the polymers of 2-aryl-1-methylenecyclopropane increases with the electron-withdrawing substituent of the aromatic group of the monomer. DSC and TG analyses of the polymer of 2-aryl-1-methylenecyclopropane show glass transition at the temperature range 153−178 °C and 5% weight loss due to thermal decomposition at 352−361 °C. The polymer of 2-etho...