3,3′-联(1,2,4-噁二唑)-5,5′-二甲醇(BOD)的水解反应机理与合成工艺  

Hydrolysis Mechanism and Synthesis Technology of 3,3′-Bi(1,2,4-oxadiazole)]-5,5′-diyldimethanol(BOD)

作　　者：薛达 王小军 徐子帅 王守飞 李永祥[1] 刘威 曹端林[1] XUE Da;WANG Xiao-jun;XU Zi-shuai;WANG Shou-fei;LI Yong-xiang;LIU Wei;CAO Duan-lin(School of Chemistry and Chemical Engineering,North University of China,Taiyuan 030051,China;Gansu Yin guang Chemical Industry Group Co,Ltd,Yinguang 730900,China;School of Environment and Safety Engineering,North University of China,Taiyuan 030051,China)

机构地区：[1]中北大学化学与化工学院,山西太原030051 [2]甘肃银光化学工业集团有限公司,甘肃银光730900 [3]中北大学环境与安全工程学院,山西太原030051

出　　处：《含能材料》2023年第11期1090-1096,共7页Chinese Journal of Energetic Materials

基　　金：山西省青年科技研究基金(202103021223179)。

摘　　要：通过理论计算的方法探究了3,3'‐联(1,2,4‐噁二唑)‐5,5'‐二甲硝酸酯(BOM)的中间体3,3'‐联(1,2,4‐噁二唑)‐5,5'‐二甲醇乙酸酯(BODM)水解生成3,3'‐联(1,2,4‐噁二唑)‐5,5'‐二甲醇(BOD)的反应机理,采用单因素实验和正交实验优化了合成工艺,并通过单晶检测、X射线衍射(XRD)、红外光谱分析(FTIR)、核磁共振、差示扫描量热法(DSC)等对BOD的结构和性能进行分析测试。结果发现,其反应机理为BODM中的—[O]—中的孤对电子与H2O中的H形成OH…O氢键,随后—[O]—[C=O]—中的O—C键断裂,H2O中的H和—OH分别与—[O]—和—[C=O]—成键形成—OH和—COOH基团。并发现BOD的晶体属于单斜晶系,空间群为C2/c,晶胞夹角α=90°,β=105.361(7)°,γ=90°,晶胞体积v=774.9(2)Å3,密度ρ=1.698 g·cm-3,其熔点和分解峰温分别为197.18℃和278.37℃。单因素实验结果表明,随着反应时间和溶剂的增加,BOD的得率先上升后趋于稳定;随着反应温度的增加,BOD的得率先缓慢上升后快速下降;随着BODM与碳酸钾的摩尔比的增加,BOD的得率先上升后下降。此外,通过正交实验优化了工艺条件,结果显示45℃下,BODM在碳酸钾的甲醇溶液中水解反应8 h,其中BODM与碳酸钾的摩尔比为15∶1,得率为94%。研究为BOD的放大及规模化生产提供了理论基础与实验参考。The reaction mechanism of intermediate 3,3´-Bis(1,2,4-oxadiazole)]-5,5´-diyldimethanol acetate(BODM)hydro-lyzed to 3,3´-Bi(1,2,4-oxadiazole)-5,5´-diyldimethanol(BOD)was investigated by theoretical calculation.The synthesis pro-cess was optimized by single factor experiment and orthogonal experiment.The structure and properties of BOD were analyzed by XRD,FTIR,NMR and DSC.It was found that the reaction mechanism was the lone pair electrons in BODM—[O]—formed an OH…O hydrogen bond with H in H2O,then the O—C bond in—[O]—[C=O]—broke,and the H and OH bonds in H2O formed—OH and—COOH group in—[O]—and—[C=O]—,respectively.and found that the crystal of BOD belong to the monoclinic system,the space group is C2/c,the cell angleα=90°,β=105.361(7)°,γ=90°,the cell volume v=774.9(2)A3,the densityρ=1.698 g·cm-3.The melting point and decomposition peak temperature were 197.18℃and 278.37℃,respectively.The results of single factor experiment showed that with the increase of reaction time and solvent,the yield of BOD increased at first and then became stable.With the increase of reaction temperature,the yield of BOD increased slowly and then decreased rapidly.With the increase of material ratio,the yield of BOD increased first and then decreased.In addition,the optimal process conditions were obtained by orthogonal experiment:BODM hydrolyzed in potassium carbonate methanol solution at 45℃for 8 h,in which the molar ratio of BODM to potassium carbonate was 15∶1,and the yield was 94%.This study provides theoretical basis and experimental reference for scaling up and large-scale production of BOD.

关 键 词：3 3'‐联(1 2 4‐噁二唑)‐5 5'‐二甲醇 水解反应机理 熔铸炸药载体 工艺优化 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O63[理学—高分子化学]