Termination and Transfer Kinetics of Acrylamide Homopolymerization in Aqueous Solution
Termination and Transfer Kinetics of Acrylamide Homopolymerization in Aqueous Solution
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DOI：
10.1021/acs.macromol.5b01921
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发表时间：
2015-10-27
期刊：
影响因子：
5.5
通讯作者：
Buback, Michael
中科院分区：
文献类型：
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作者：
Kattner, Hendrik;Buback, Michael
采用单脉冲激光聚合电子顺磁共振（SP-PLP-EPR）方法对丙烯酰胺水溶液聚合进行了详细的动力学分析。10和20重量% AAm的高时间分辨SP-PLP-EPR实验首先在-5 ° C下进行，其中仅发生二次传播自由基（SPR）。在第二步中，在较高温度下测量了由SPRs通过反咬产生的中链自由基（MCR）的时间演化。终止动力学，包括链长依赖性终止的SPR，SPRs的反咬率，和MCRs的传播速率进行了测定。从SP PLP-EPR的速率系数结合已知的SPR的增长速率系数，使AAm自由基聚合在水溶液中的动力学和产品性能的模拟。
The single pulse pulsed laser polymerization electron paramagnetic resonance (SP-PLP-EPR) method affords the detailed kinetic analysis of acrylamide polymerization in aqueous solution. Highly time-resolved SP-PLP-EPR experiments for 10 and 20 wt % AAm were first carried out at -5 degrees C, where only secondary propagating radicals (SPRs) occur. In a second step, the time evolution of midchain radicals (MCRs), produced from SPRs by backbiting, was measured at higher temperatures. The termination kinetics, including chain-length dependent termination of SPRs, the backbiting rate of SPRs, and the propagation rate of MCRs were determined. The rate coefficients from SP PLP-EPR in conjunction with the known propagation rate coefficient of SPRs, enable the simulation of the kinetics and product properties of AAm radical polymerizations in aqueous solution.