Development of Cyclic Propagation Kinetics for Modeling the Nitroxide-mediated Radical Copolymerization of Styrene-Divinylbenzene
Development of Cyclic Propagation Kinetics for Modeling the Nitroxide-mediated Radical Copolymerization of Styrene-Divinylbenzene
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DOI：
10.1002/mren.201300105
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发表时间：
2014-04-01
影响因子：
1.5
通讯作者：
Giudici, Reinaldo
中科院分区：
文献类型：
--
作者：
Aguiar, Leandro G.;Goncalves, Miguel A. D.;Giudici, Reinaldo
提出了一种包括循环传播（环化）的动力学模型，用于硝基氧介导的苯乙烯-二乙烯基苯自由基共聚。该方法涉及单元序列的平衡，这些单元连接同一聚合物链中存在的自由基中心和侧双键。环化的速率常数被认为是序列长度的函数。发现溶液和悬浮液控制共聚的模型预测与实验数据之间具有良好的一致性。最小环（3个单体单元）的环化速率常数在90℃下估计为700s(-1)，活化能估计为32500calmol(-1)。
A kinetic model including the cyclic propagation (cyclization) is proposed for the nitroxide-mediated radical copolymerization of styrene-divinylbenzene. The method involves a balance of sequences of units, which connect a radical center and a pendant double bond present in the same polymer chain. The rate constant for cyclization was considered a function of the sequence length. Good agreement between the model predictions and experimental data for solution and suspension controlled copolymerizations was found. The rate constant of cyclization for the smallest ring (3 monomeric units) was estimated to be 700s(-1) at 90 degrees C, and the activation energy was estimated to be 32500calmol(-1).