有机过氧化物的热危险性辨识研究  

New effective approach to identifying dangerous thermal behavior of organic peroxides

作　　者：其乐木格[1] 张凤[2] 

机构地区：[1]呼和浩特职业学院高职高专研究所,呼和浩特010053 [2]中国民航管理干部学院机场管理系,北京100102

出　　处：《安全与环境学报》2012年第3期177-181,共5页Journal of Safety and Environment

基　　金：内蒙古自治区教育厅研究项目(NJC07186)

摘　　要：运用Gaussian 98量子化学程序包中考虑了电子相关性的密度泛函理论(DFT)的B3LYP方法,在6-311+G(3df)水平上根据分子结构与化学键的关系,计算得到了过氧化苯甲酰和过氧化甲乙酮两种有机过氧化物分解反应的反应物、中间物和产物的总能量数据,求出这两种有机过氧化物分解反应的最大反应热,应用CHETAH程序中最大分解热的判断标准预测这两种有机过氧化物的热危险性均为中等。同时使用绝热加速量热技术对这两种有机过氧化物的热危险性进行分析,通过绝热温升、自加速分解温度、单位质量产生的压力等参数可以得出,两种有机过氧化物的热危险性均为中等。这两种方法可以互为验证,用来作为辨识有机过氧化物的热危险性的依据。The paper intends to provide a new effective approach to identifying dangerous thermal behavior of organic peroxides.Our research purpose is to study and search for a new way to identify such dangerous thermal behaviors of theirs both from the anger of theoretical calculations and experimental verifications,such as those of BPO and MEKPO.To reach our research goal,we have worked out the total energy data of the reactants,intermediates and the final products of the two drugs in their decomposition process,in accordance with the relation between the molecular structures and chemical bonds of theirs by means of Gaussinan-98 quantum chemical program package.At the same time,we have disclosed the strongest decomposition reaction heat data of the two organic peroxides and forecasted their thermal decomposition danger by using the criteria in the CHETAH diagram and their electronic correlation at 6-311＋G（3df） level based on the Density Functional Theory（DFT） and the B3LYP method.The results of the theoretical calculations reveal that the thermal hazards both of BPO and MEKPO are moderate.On the other hand,we have done the experimental analyses of the peroxides by using the adiabatic accelerating rate calorimetric heat technology.The data obtained from the ARC tests,such as the adiabatic temperature rise,the self-accelerating decomposition temperature and the decomposition pressure per unit mass all demonstrate that the hazardous risk both BPO and MEKPO are likely to cause remains moderate too.Thus,both the theoretical calculations and the experimental examination are in close conformity with each other,that is to say,the two ways are equally effective for identifying the thermal dangerous behaviors of the two organic compounds.

关 键 词：安全工程 有机过氧化物 热危险性 量子化学 绝热加速量热仪 

分 类 号：X932[环境科学与工程—安全科学]