摘要
用AM1方法计算了马来酸酐、羟基自由基及其加成产物α-羟基丁二酸酐基自由基的电子结构、电荷分布和键级.应用前线轨道理论和成键三原则研究了羟基自由基引发下马来酸酐聚合过程中α-羟基丁二酸酐基自由基活性中间体参与反应的可能性及其自由基聚合反应机理.计算结果表明:马来酸酐基态分子的HOMO和LUMO分别对应于双键CC的成键π-MO和反键π -MO;马来酸酐的羟基自由基加成反应活化能计算值为55 7kJ/mol;马来酸酐在羟基自由基引发下的自由基聚合产物是链式结构,与实验事实相符.
The electronic structures,charge distribution and bond orders in maleic anhydride (MA),hydroxyl radical,and α-hydroxysuccinic anhydride radical(HOSA) have been calculated by using an AM1 method.The possibility of reaction of active HOSA radical on polymerization process of MA induced by hydroxyl radical and the mechanism of radical polymerization of maleic anhydride were studied on the basis of the Frontier Orbital Theory and Three Bonding Principles.Calculation results show that the HOMO and LUMO of MA are (π-bonding) and π~*-antibonding MOs of bond CC respectively.The calculated activation energy on the addition reaction between MA and hydroxyl radical is 55.7 kJ/mol.The theoretical-calculation structure of radical polymerization product of MA induced by hydroxyl radical is of the chain,which verify nicely the experimental findings.
出处
《分子科学学报》
CAS
CSCD
2004年第1期33-37,共5页
Journal of Molecular Science
基金
南京理工大学科研启动基金资助项目(AB41258)
