合成聚甲醛二甲基醚反应热力学的理论计算TheoreticalCalculations.PDFVIP

2009 年第67 卷 化 学 学 报 Vol. 67, 2009 第8 期, 767～772 ACTA CHIMICA SINICA No. 8, 767～772 ·研究论文· 合成聚甲醛二甲基醚反应热力学的理论计算 雷艳华 孙 清 陈兆旭 沈俭一* (南京大学化学化工学院 南京 210093) 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. 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 Theoretical Calculations on the Thermodynamics for the Synthesis Reactions of Polyoxymethylene Dimethyl Ethers Lei, Yanhua Sun, Qing Chen, Zhaoxu Shen, Jianyi* (Department of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093) Abstract 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. Keywords polyoxymethylene dimethyl ether (PODE); thermodynamic parameter; thermodynamic equilib- rium conversion; density function theory (DFT); isodesmic reaction 聚甲醛二甲基醚(polyoxymethylene dimethyl ethers, 专利涉及PODE 的合成, 为德国BASF 公司申请[3]. 在 简称 PODE)