Lithium diisopropylamide as initiator for the anionic polymerization of methacrylates
Lithium diisopropylamide as initiator for the anionic polymerization of methacrylates
复制标题
二异丙基酰胺锂作为甲基丙烯酸酯阴离子聚合引发剂
DOI：
10.1021/ma961394a
复制
发表时间：
1997
期刊：
影响因子：
5.5
通讯作者：
R. Jerome
中科院分区：
文献类型：
--
作者：
S. Antoun;P. Teyssie;R. Jerome
研究了甲基丙烯酸甲酯（MMA）、甲基丙烯酸叔丁酯（tBuMA）、（二甲氨基）甲基丙烯酸乙酯（DMAEMA）和甲基丙烯酸甘油酯（GMA）在- 78℃THF中以二异丙酰胺锂（LDA）和α-异丁酸锂乙酯（Li-EIB）与LiCl络合为引发剂的阴离子聚合反应。连接Li-EIB是甲基丙烯酸酯阴离子聚合中烯酸酯扩散的模型，与之相比，连接LDA具有相当的引发效率（>90%），并且产生的聚合物具有可预测的分子量和窄分子量分布（MWD < 1.1）。与其他聚甲基丙烯酸酯相比，LiCl对聚甲基丙烯酸酯MWD的影响较小。在没有LiCl的情况下，已经很窄的MWD可能是由于生长的聚GMA的倒数第二单元(s)的氧烷基团对离子的分子内配位造成的。作为控制良好的阴离子聚合的直接结果…
The anionic polymerization of a series of methacrylates, i.e. methyl methacrylate (MMA), tert-butyl methacrylate (tBuMA), (dimethylamino)ethyl methacrylate (DMAEMA), and glycidyl methacrylate (GMA), has been investigated in THF at −78 °C, by using both lithium diisopropylamide (LDA) and α-lithioethyl isobutyrate (Li-EIB) complexed with LiCl as initiators. Compared to ligated Li-EIB, which is a model for the propagating enolate in the methacrylate anionic polymerization, ligated LDA has quite a comparable initiation efficiency (>90%) and gives rise to polymers with a predictable molecular weight and a narrow molecular weight distribution (MWD < 1.1). The effect of LiCl on the MWD of poly-GMA is less pronounced compared to the other polymethacrylates. An already narrow MWD in the absence of LiCl might be accounted for by an intramolecular coordination of the ion pair by the oxirane group of the (ante)penultimate unit(s) of growing poly GMA. As a direct consequence of the well-controlled anionic polymerizati...