Copolymerization kinetics of methyl methacrylate-styrene obtained by PLP-MALDI-ToF-MS.
Copolymerization kinetics of methyl methacrylate-styrene obtained by PLP-MALDI-ToF-MS.
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DOI：
10.1021/ja0579715
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发表时间：
2006-03
影响因子：
15
通讯作者：
R. Willemse;A. V. van Herk
中科院分区：
文献类型：
--
作者：
R. Willemse;A. V. van Herk
采用MALDI-ToF-MS技术和脉冲激光聚合技术相结合的方法研究了苯乙烯-甲基丙烯酸甲酯共聚物体系的传输速率系数。对于第一次，完整的信息有关的终止模式，光引发剂衍生的自由基，共聚物的分子量，化学组成，和共聚速率的反应性是相互关联的。在15.2摄氏度的温度下，通过具有不同频率的受激准分子脉冲激光器，用不同的苯乙烯浓度在本体中进行聚合。化学组成分布和分子量分布由MALDI-ToF-MS确定。数据拟合到隐式倒数第二单元模型，并导致苯乙烯-甲基丙烯酸甲酯共聚物系统的单体和自由基竞聚率的新的点估计：r（St）= 0.517，r（MMA）= 0.420，s（St）= 0.296，s（MMA）= 0.262。Monte Carlo模拟和所得结果之间的比较进一步证实了脉冲激光共聚实验与MALDI-ToF-MS的非常成功的结合。所得结果被认为是迄今为止最准确和完整的共聚参数集。
The combination of MALDI-ToF-MS and pulsed laser polymerization has been used to study the propagation rate coefficients for the copolymer system styrene-methyl methacrylate. For the first time, complete information regarding mode of termination, reactivity of photoinitiator-derived radicals, copolymer molecular mass, chemical composition, and copolymerization rates is obtained interrelated. The polymerizations were carried out in bulk with varying styrene concentrations at a temperature of 15.2 degrees C by an excimer pulsed laser with varying frequencies. Both chemical composition distributions and molecular weight distributions were determined by MALDI-ToF-MS. The data were fitted to the implicit penultimate unit model and have resulted in new point estimates of the monomer and radical reactivity ratios for the copolymer system styrene-methyl methacrylate: r(St) = 0.517, r(MMA) = 0.420, s(St) = 0.296, s(MMA) = 0.262. Comparison between Monte Carlo simulations and the obtained results further confirmed the very successful combination of pulsed laser copolymerization experiments with MALDI-ToF-MS. The obtained results are believed to be the most accurate and complete set of copolymerization parameters to date.