DFT法研究三聚甲醛开环聚合热力学

DFT Method Study on Thermodynamics of Ring Opening Polymerization

开环聚合是高分子化学的重要组成部分,环醚的开环聚合反应是开环聚合反应中具有代表性的一类。本文利用DFT方法,使用高斯量子化学计算软件,通过对1,3-二氧六环、1,4二氧六环、1,3,5-三氧六环等单体的结构优化和能量计算,获得了这些单体的结构数据和开环聚合的热力学数据。计算结果表明:三元环、四元环状单体张力较大,开环聚合倾向较大。六元环中,1,3,5-三氧六环由于氧原子斥力较大,能量较高易于开环。

Ring opening polymerization is an important part of polymer chemistry.Ring opening polymerization of ring ethers is a representative type of ring opening polymerization.In this paper,DFT method and Gauss quantum chemistry calculation software are used to obtain the structural data and thermodynamic data of ring opening polymerization of dioxane for propylene oxide,tetrahydrofuran,1,3-dioxane,1,4-dioxane,1,3,5-trioxane and other monomers through structural optimization and energy calculation.The calculation results indicate that the tension of ternary and quaternary cyclic monomers is high,and the tendency for ring opening polymerization is greater.Among the six membered rings,1,3,5-dioxane is prone to ring opening due to its high energy caused by the strong repulsion of oxygen atoms.