【摘要】 采用分子力学和半经验量子化学的方法 ,计算出了数十种有机过氧化物氧氧键均裂的键离解能 ,以及过氧化物生成的自由基的氧净电荷及其校正值 .数据的多重线性回归证明 ,影响有机过氧化物引发剂活性(常用 1 0h HLT表示 )的主要因素为自由基的电性和空间效应 ,这两者可以用自由基的氧净电荷及其校正值来表征 .在同种溶剂中 ,过氧化物生成的两个自由基的氧净电荷及其校正值 ,这四个因素与其半分解温度之间有较好的相关性 .这种相关性可以用来预测过氧化物的 1 0h HLT值 .更多还原

【Abstract】 In order to explore structural specialty on reactivity of peroxides,the oxygen\|oxygen bond dissociation energy,the oxygen net charges and the calibration charges of free radicals have been caculated via molecular mechanics and AM1 method for decades of organic peroxides.Multiple linear regression was performed for the calculated data with 10h\|HLT,which is a kinetic parameter in literature.Results show that the oxygen\|oxygen bond dissociation energies of the examined peroxides are not correlated with their 10h\|HLT parameters.Since the thermal homolytical cleavage of the peroxide is a reversal process,it includes the decomposition of the parent peroxide and the recombination of the oxygen\|centered free radicals.The interaction of the free radicals in the recombination was considered significant.Obtained results indicate that the electronic structure and the spatial topology of radicals mostly influence reactivity of the peroxides.The more the absolute of oxygen charge densities in the free radicals,the easier the dissociation of the parent peroxide.It was found that the oxygen net charge and the calibration charge of radicals play the key roles in characterization of the reactivity of the peroxides.In the same solvent the four factor linear regression is mostly obeyed between the 10h\|HLTs of the parent peroxides and the two oxygen net charges and the two calibration charges for two free radicals.The 10h\|HLT values have thus been predicted by using a correlation with the four factors.更多还原