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Ring-Opening Polymerization of Propylene Oxide by Double Metal Complex in Micro-Reactor

机译:微反应器中双金属配合物对环氧丙烷的开环聚合

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The ring-opening polymerization of propylene oxide catalyzed by double metal complex (DMC) is carried out in continuous micro-reactor (C-MR). It is found that the monomer conversion at the C-MR outlet is usually 100% within 2 min of average residence time, which means that the polymerization rate in the C-MR is faster than that in a traditional semi-continuous tank reactor. However, the induction period still exists in the polymerization in C-MR, but can be shortened by increasing the reaction temperature or the micro-reactor length. The mechanism of monomer coordination and ring opening on DMC during the induction period is confirmed by the H-1 NMR analysis of the samples obtained under very short average residence time. The molecular weight distribution (MWD) of product from C-MR is generally narrow, which indicates that the process still maintain the characteristics of the "living" polymerization. That is, there is a very high rate ratio of chain transfer to chain propagation provided by the DMC catalyst. However, with the same average residence time, the MWD of product from the longer C-MR is broader, which can be attributed to the increase of the chain propagation rate caused by rise of pressure.
机译:双金属络合物(DMC)催化的环氧丙烷的开环聚合反应是在连续微反应器(C-MR)中进行的。发现在C-MR出口处的单体转化率通常在平均停留时间的2分钟内为100%,这意味着C-MR中的聚合速率比传统的半连续釜式反应器中的聚合速率更快。然而,在C-MR中聚合中仍存在诱导期,但是可以通过提高反应温度或微反应器长度来缩短诱导期。通过在非常短的平均停留时间下获得的样品的H-1 NMR分析证实了诱导期间DMC上单体配位和开环的机理。来自C-MR的产物的分子量分布(MWD)通常较窄,这表明该方法仍保持“活性”聚合的特征。即,由DMC催化剂提供的链转移与链传播的比率非常高。但是,在相同的平均停留时间下,来自较长C-MR的产物的MWD较宽,这可归因于因压力升高而引起的链增长速率的增加。

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