丙交酯合成过程的理论及实验研究.pdfVIP

2006 年第64 卷 化 学 学 报 Vol. 64, 2006 第10 期, 1011～1016 ACTA CHIMICA SINICA No. 10, 1011～1016 ·研究论文· 丙交酯合成过程的理论及实验研究 李文斌 吴文鹏 娄 帅 张普玉* (河南大学精细化学与工程研究所 开封 475001) 摘要 采用密度泛函方法研究了丙交酯的合成过程, 优化了合成过程中可能出现的化合物的几何构型, 分析了各化合物 的振动频率和偶极矩. 在B3LYP/6-31G*和B3LYP/6-311 ＋G*水平上进行了各化合物的能量计算, 得到了所设计的各模型 反应的焓变和吉布斯自由能变. 结果表明, 所选择的各模型反应为吸热反应且近似可逆, 水的控制对丙交酯的形成很重 要. 根据量化计算结果与丙交酯合成实验中不同阶段反应体系红外谱图的变化, 提出了丙交酯合成的可能机理. 关键词 丙交酯; 密度泛函理论; 红外光谱; 合成机理 Theoretical and Experimental Studies on Synthesis of Lactide LI, Wen-Bin WU, Wen-Peng LOU, Shuai ZHANG, Pu-Yu* (Institute of Fine Chemistry and Engineering, Henan University , Kaifeng 475001) Abstract Theoretical studies on synthetic process of lactide were carried out with density functional theory and the geometries of compounds maybe to appear in reactive system were optimized. The changes of en- thalpy and Gibbs free energy were computed at B3LYP/6-31G* and B3LYP/6-311 ＋G* levels of theory, suggesting that the selected model reactions should be endothermal and approximately reversible. The re- sults indicated that control of water in the reaction system was very important to the formation of lactide. By combination of the results of quantum computation with the infrared spectra obtained at various synthetic stage, the possible synthetic mechanism was proposed. Keywords lactide; density functional theory; infrared spectrum; synthetic mechanism 聚乳酸是目前研究最广泛、最具开发潜力的可生物 理论对合成过程进行了模拟计算, 并用红外光谱表征了 [1] 反应体系, 通过结合两者的结果提出了可能的合成机 降解材料 , 其聚合方法主要有直接法、间接法两种. 直 接法是乳酸经过酯化缩合脱除小分子水得到聚合物, 通 理.