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Propagation Kinetics of Isoprene Radical Homopolymerization Derived from Pulsed Laser Initiated Polymerizations
Macromolecular Reaction Engineering ( IF 1.8 ) Pub Date : 2019-09-18 , DOI: 10.1002/mren.201900030 Brian Büren 1 , Florian Brandl 1 , Sabine Beuermann 1
Macromolecular Reaction Engineering ( IF 1.8 ) Pub Date : 2019-09-18 , DOI: 10.1002/mren.201900030 Brian Büren 1 , Florian Brandl 1 , Sabine Beuermann 1
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The propagation kinetics of isoprene radical polymerizations in bulk and in solution are investigated via pulsed laser initiated polymerizations and subsequent polymer analyses via size‐exclusion chromatography, the PLP‐SEC method. Because of low polymerization rate and high volatility of isoprene, the polymerizations are carried out at elevated pressure ranging from 134 to 1320 bar. The temperatures are varied between 55 and 105 °C. PLP‐SEC yields activation parameters of kp (Arrhenius parameters and activation volume) over a wide temperature and pressure range that allow for the calculation of kp at technically relevant ambient pressure conditions. The kp values determined are very low, e.g., 99 L mol−1 s−1 at 50 °C, which is even lower than the corresponding value for styrene polymerizations. The presence of a polar solvent results in a slight increase of kp compared to the bulk system. The kp values reported are important for determining rate coefficients of other elemental reactions from coupled parameters as well as for modeling isoprene free‐radical polymerizations and reversible deactivation radical polymerization with respect to tailored polymer properties and optimizing the polymerization processes.
中文翻译：
脉冲激光引发聚合反应衍生的异戊二烯自由基均聚反应的动力学
异戊二烯自由基聚合在本体和溶液中的传播动力学通过脉冲激光引发的聚合反应进行研究，随后通过尺寸排阻色谱法（PLP-SEC方法）进行聚合物分析。由于低聚合速率和异戊二烯高挥发性，因此聚合反应在134至1320 bar的高压下进行。温度在55至105°C之间变化。PLP-SEC可以在很宽的温度和压力范围内产生k p的激活参数（阿累尼乌斯参数和激活体积），从而可以在技术上相关的环境压力条件下计算k p。确定的k p值非常低，例如99 L mol -1s -1在50°C时，甚至低于苯乙烯聚合的相应值。与本体系统相比，极性溶剂的存在导致k p略有增加。报告的k p值对于根据耦合参数确定其他元素反应的速率系数以及对异戊二烯自由基聚合和可逆减活自由基聚合进行建模（针对定制的聚合物特性）和优化聚合过程非常重要。
更新日期：2019-09-18
中文翻译：
脉冲激光引发聚合反应衍生的异戊二烯自由基均聚反应的动力学
异戊二烯自由基聚合在本体和溶液中的传播动力学通过脉冲激光引发的聚合反应进行研究，随后通过尺寸排阻色谱法（PLP-SEC方法）进行聚合物分析。由于低聚合速率和异戊二烯高挥发性，因此聚合反应在134至1320 bar的高压下进行。温度在55至105°C之间变化。PLP-SEC可以在很宽的温度和压力范围内产生k p的激活参数（阿累尼乌斯参数和激活体积），从而可以在技术上相关的环境压力条件下计算k p。确定的k p值非常低，例如99 L mol -1s -1在50°C时，甚至低于苯乙烯聚合的相应值。与本体系统相比，极性溶剂的存在导致k p略有增加。报告的k p值对于根据耦合参数确定其他元素反应的速率系数以及对异戊二烯自由基聚合和可逆减活自由基聚合进行建模（针对定制的聚合物特性）和优化聚合过程非常重要。
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