Viscosity Effects on the Thermal Decomposition of Bis(perfluoro-2-<i>N</i>-propoxypropionyl) Peroxide in Dense Carbon Dioxide and Fluorinated Solvents
作者:W. Clayton Bunyard、John F. Kadla、Joseph M. DeSimone
DOI:10.1021/ja0103344
日期:2001.8.1
The thermal decomposition of the free-radical initiator bis(perfluoro-2-N-propoxyprionyl) peroxide (BPPP) was studied in dense carbon dioxide and a series of fluorinated solvents. For the fluorinated solvents, the observed first-order decomposition rate constants, k(obs), increased with decreasing solvent viscosity, suggesting a single-bond decomposition mechanism. The k(obs) values are comparatively
在浓二氧化碳和一系列氟化溶剂中研究了自由基引发剂双 (全氟-2-N-丙氧基丙氧基) 过氧化物 (BPPP) 的热分解。对于氟化溶剂,观察到的一级分解速率常数 k(obs) 随着溶剂粘度的降低而增加,表明存在单键分解机制。k(obs) 值在浓二氧化碳中相对较大,类似于从氟化溶剂中的分解动力学推断出的“零粘度”速率常数。分解活化参数证明了活化焓与活化熵在溶剂粘度变化时的补偿行为。