新型耐高温树脂热稳定性的理论研究  

Theoretical Studies on the Thermal Stability of New Types of High Temperature Resistant Resins

作　　者：吴小伟[1] 朱卫华[1] WU Xiaowei;ZHU Weihua(Institute for Computation in Molecular and Materials Science,School of Chemistry and Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)

机构地区：[1]南京理工大学化学与化工学院,分子与材料计算研究所,南京210094

出　　处：《功能高分子学报》2021年第6期548-553,共6页Journal of Functional Polymers

摘　　要：采用密度泛函理论(DFT)对系列新型耐高温硅烷-芳炔树脂分子、含芳杂环树脂分子和含氰基树脂分子中主要键的键离解能(BDE)进行了系统研究。结果表明,含不同基团树脂分子的热稳定性具有显著差异。含氰基树脂分子比硅烷-芳炔树脂分子和含芳杂环树脂分子的热稳定性更高,向树脂分子中引入氰基更有利于增强树脂的耐高温性能。The development of new resins with high heat resistance and excellent processing properties is of great significance to aerospace,communications,and electronics fields.In this work,density functional theory(DFT)is used to systematically study the bond dissociation energy(BDE)of main bonds in a series of new heat-resistant silane-arylacetylene resin,aromatic heterocyclic-containing resin,and cyano-containing resin molecules.The DFT-B3LYP functional and 6-31g(d,p)basis set are adopted to make all resin molecules relax fully.The vibrational analysis results show that all resin molecules have no imaginary frequency,indicating that they correspond to the stable configuration on their potential energy surfaces.Then,BDEs of the main chemical bonds in all resin molecules are calculated.This work mainly studies the thermal stability of resin monomer molecules,so the thermal stability of the monomer molecules can be measured by calculating BDE of the main bonds in the resin monomer molecules.In fact,the curing reaction of the resin monomer molecules at high temperature usually occurs on the branches,while the ring remains unchanged.The heterocyclic ring and benzene ring are aromatic,and BDEs of the bonds on the rings are higher than those of the non-cyclic bonds.Therefore,BDEs of the bonds on the rings in the resin monomer molecules are not considered in this work.At the same time,the reactants and free radical products are optimized and the vibrational analysis is performed.The results show that the cyano-containing resin molecules have higher thermal stability than the silane-aryne-containing resin molecules and aromatic heterocyclic-containing resin molecules,indicating that the introduction of cyano groups into the resin molecules is more helpful for improving their thermal stability than the introduction of silane-arylalkynyl and aromatic heterocycles groups.Our studies find the weakest bond in each resin molecule and reveal the essence of its thermal stability at the microscopic level,which provide a theoretical basi

关 键 词：密度泛函理论 键离解能 树脂 热稳定性 

分 类 号：O63[理学—高分子化学]