Effect of Intramolecular Transfer to Polymer on Stationary Free-Radical Polymerization of Alkyl Acrylates, 5 – Consideration of Solution Polymerization up to High Temperatures†
Effect of Intramolecular Transfer to Polymer on Stationary Free-Radical Polymerization of Alkyl Acrylates, 5 – Consideration of Solution Polymerization up to High Temperatures†
复制标题
分子内转移到聚合物对丙烯酸烷基酯固定自由基聚合的影响，5 – 高温下溶液聚合的考虑†
DOI：
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发表时间：
2010
期刊：
影响因子：
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通讯作者：
C. Bruni
中科院分区：
文献类型：
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作者：
A. N. Nikitin;R. Hutchinson;Wei Wang;G. Kalfas;J. R. Richards;C. Bruni
丙烯酸丁酯溶液聚合已在 80-170 °C 的单体和引发剂水平范围内进行了研究。开发了 PREDICI 模型来描述实验，同时考虑了链背咬、β-断裂和大分子单体的添加。该模型用于估计β-断裂速率系数的阿伦尼乌斯参数[A(k β ) = (1.49 ± 0.28) x 10 9 s -1 , E a (k β ) = 63.9 ± 0.9 kJ · mol -1 ]，二级自由基和中链自由基的终止速率系数之比[A (k t /k t t ) = 0.74 ± 0.08, E a (k t /k t t ) = -(11.2 ± 0.5)kJ · mol -1 ] 以及通过将模拟的依赖性与实验数据拟合，得到二甲苯链转移常数 [A(Ctrs) = 107 ± 13, E a (Ctrs) = 35.4 ± 0.8 kJ · mol -1 ]。
Butyl acrylate solution polymerization has been studied at 80-170 °C over a range of monomer and initiator levels. A PREDICI model has been developed to describe the experiments, taking into account chain backbiting, β-scission, and addition of macromonomer. The model is used to estimate Arrhenius parameters for the rate coefficients of β-scission [A(k β ) = (1.49 ± 0.28) x 10 9 s -1 , E a (k β ) = 63.9 ± 0.9 kJ · mol -1 ], for the ratio of the termination rate coefficients of secondary and midchain radicals [A (k t /k t t ) = 0.74 ± 0.08, E a (k t /k t t ) = -(11.2 ± 0.5)kJ · mol -1 ] and for the constant of chain transfer to xylene [A(Ctrs) = 107 ± 13, E a (Ctrs) = 35.4 ± 0.8 kJ · mol -1 ] by fitting simulated dependencies to the experimental data.