Activated anionic ring-opening polymerization of ε-caprolactam with magnesium di(ε-caprolactamate) as initiator: effect of magnesium halides

被引：0
作者：
Yulia A. Piskun
Irina V. Vasilenko
Ludmila V. Gaponik
Sergei V. Kostjuk
机构：
[1] Research Institute for Physical Chemical Problems of the Belarusian State University,
来源：
Polymer Bulletin | 2012年 / 68卷
关键词：
Ring-opening polymerization; Anionic polymerization; ε-Caprolactam; Poly(ε-caprolactam); Magnesium di(ε-caprolactamate);
D O I：
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摘要：
The activated anionic ring-opening polymerization of ε-caprolactam initiated by 0.35 mol% of combined initiator, i.e., equimolar mixture of magnesium di(ε-caprolactamate) (CL2Mg) with magnesium halides (MgCl2, MgBr2, and MgI2) as well as of ε-caprolactam magnesium bromide (CLMgBr) in the presence of 0.35 mol% of N-acetyl-ε-caprolactam as an activator has been investigated in the temperature range 140–200 °C. It was found that the reaction rate increased while the apparent activation energy decreased in the following series: CL2Mg/MgCl2 < CL2Mg/MgBr2 ~ CLMgBr < CL2Mg/MgI2. In addition, the poly(ε-caprolactam)s prepared with CL2Mg/MgX2 (MgX2 = MgCl2, MgBr2, and MgI2) are characterized by slightly higher thermal stability than polymers obtained with CLMgBr as initiator. These observations were explained in terms of the coordination of Lewis acids (MgX2, where X = Cl, Br, and I) with imide carbonyl of N-acyllactam end groups leading to the increase of their reactivity and stability.
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页码：1501 / 1513
页数：12
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