合成聚甲醛二甲基醚反应热力学的理论计算  

Theoretical Calculations on the Thermodynamics for the Synthesis Reactions of Polyoxymethylene Dimethyl Ethers

作　　者：雷艳华[1] 孙清[1] 陈兆旭[1] 沈俭一[1] 

机构地区：[1]南京大学化学化工学院,南京210093

出　　处：《化学学报》2009年第8期767-772,共6页Acta Chimica Sinica

基　　金：中国石油化工股份有限公司上海石油化工研究院及科技部973(No.2005CB221400)资助项目

摘　　要：采用密度泛函理论(DFT)方法在B3LYP/6-31+G(d,p)水平上对聚甲醛二甲基醚(PODE)系列化合物进行了全优化和振动分析计算,获得了该系列化合物的最优构型及热力学函数值.通过设计等键反应计算了PODE的生成热,并进一步计算了生成PODE的反应平衡常数及转化率,进而判断这些反应的热力学可行性.Fully optimized calculation and frequency analysis for polyoxymethylene dimethyl ethers （PODE） were carried out using a density function theory （DFT） method at the B3LYP/6-31＋G（d,p） level. The structural and thermodynamic parameters of PODE were obtained. In addition, the standard enthalpies of PODE were calculated by designing the isodesmic reactions. Accordingly, the equilibrium constants and equilibrium conversions for the synthesis reactions of PODE were derived, according to which the thermo- dynamic feasibility for the synthesis of PODE with different feed stocks was assessed.

关 键 词：聚甲醛二甲基醚(PODE) 热力学参数 热力学平衡转化率 密度泛函理论(DFT) 等键反应 

分 类 号：O631.3[理学—高分子化学]