Theoretical study on Variety of substituent effects Influence the Synthesis of High Energy Density Material 1,3,3-trinitroazetidine (TNAZ)

• Main Authors: Kuang-Hung Yen, 顏光宏
• Other Authors: Min-Hsien Liu
• Format: Others
• Language: zh-TW
• Published: 2014
• Online Access: http://ndltd.ncl.edu.tw/handle/87705964988735938201

碩士 === 國防大學理工學院 === 化學工程碩士班 === 102 === This study is aimed at the simulation modeling of synthesis of 1,3,3-trinitro azetidine （TNAZ） high-energy compound. Based on the experimental nitrometane and 1,3-dihalo-2-propanol raw material methods in latest literatures, we suggested reasonably reaction mechanisms. Using quantum mechanical theory, i.e.,electronic density functional theory（DFT）B3LYP/6-31G（d,p） in the version of Gaussian 09 program, we have completed optimization work for all species in relatrd reaction stage and have obtained energy barrier data, which were referred to pick out the more feasible reaction path ways. From the research results：Nitromethane was used to react with formaldehyde through ionic type transition to produce 2,2-dinitro-1,3-propandiol,followed by reacting with hydrogen bromide to produce 1,3-dibromo-2,2-dinitro propane; further reacting with tertiary amine to produce 1-tertiary amino-3,3-dinitro azetidine, and undergo nitration to obtain TNAZ. Substituent effect of some atomic groups were found in this part of synthesis modeling, and a total activation energy of 1386.6 kJ/mol has to be conquered to complete the reaction. Furthermore, synthesis modeling with 1,3-dihalo-2-propanol raw material method, the suggested reaction routes could be bromination of glycerol to 1,3-dibromo-2-propanol; followed by reacting with nitromethane to undergo amination, and further cyclization, oxidation, oximization, nitration in sequence to produce the target TNAZ product. An overall 1163.5 kJ/mol of energy barrier has to be crossed over in this part of computation. Keywords：1,3,3 - trinitro azetidine（TNAZ）, density functional theory（DFT）, substituent effect, activation energy, amination reaction.