偕二硝基不敏感增塑剂的合成与性能  

Synthesis and properties of geminal dinitro insensitive plasticizers

作　　者：刘亚静[1] 高福磊[1] 汪营磊[1] 赵宝东 陈斌[1] 尉涛[1] LIU Ya-jing;GAO Fu-lei;WANG Ying-lei;ZHAO Bao-dong;CHEN Bin;YU Tao(Xi’an Modern Chemistry Research Institute,Xi’an 710065,China)

机构地区：[1]西安近代化学研究所,陕西西安710065

出　　处：《应用化工》2020年第7期1693-1696,共4页Applied Chemical Industry

基　　金：国家自然科学基金(21303133,21875185)。

摘　　要：2,2-二硝基丙醇分别与乙酸、丙酸、正丁酸经酯化反应,合成2,2-二硝基丙醇乙酸酯、2,2-二硝基丙醇丙酸酯、2,2-二硝基丙醇丁酸酯三种新型偕二硝基酯类增塑剂。利用FTIR、NMR和元素分析等对偕二硝基酯类增塑剂进行了结构表征;考察了催化剂浓硫酸用量、反应物料比及反应时间对产物收率和纯度的影响。结果表明,2,2-二硝基丙醇乙酸酯较佳合成条件为:浓硫酸用量3%,2,2-二硝基丙醇与乙酸摩尔比为1∶1.10,酯化反应时间6 h。测试了所合成的三种新型增塑剂的密度、热分解温度、玻璃化转变温度、感度等性能,并计算了生成焓和溶解度参数。其中2,2-二硝基丙醇乙酸酯的性能如下:密度1.319 g/cm^3,溶解度参数20.994 J1/2/cm^3/2,玻璃化转变温度-94.4℃,热分解峰温为254.9℃,生成焓414.5 kJ/mol,摩擦感度4%,撞击感度H50>125.9 cm。Three novel geminal dinitro ester plasticizers 2,2-dinitropropyl acetate,2,2-dinitropropyl propionate and 2,2-dinitropropyl butyrate were synthesized by the esterification of 2,2-dinitropropanol with acetic acid,propionic acid,and butyric acid,respectively.The structures of designed and synthesized germinal dinitro ester plasticizers were characterized by FTIR,NMR and elemental analysis;The effects of catalyst dosage,the molar ratio of raw materials and reaction time on the reaction yield and purity were investigated.The result showed that the optimized reaction conditions for 2,2-dinitropropyl acetate are determined as follows:the dosage of concentrated sulfuric acid is 3%,the molar ratio of 2,2-dinitropropanol and acid is 1∶1.10,and the esterification reaction time is 6 h.Their density,peak temperature of thermal decomposition,glass transition temperature and sensitivities were measured,and enthalpy of formation and solubility parameter were calculated.The properties of 2,2-dinitropropyl acetate are as follows:density is 1.319 g/cm^3,solubility parameter is 20.994 J 1/2/cm^3/2,glass transition temperature is-94.4℃,peak temperature of thermal decomposition is 254.9℃,enthalpy of formation is 414.5 kJ/mol,friction sensitivity is 4%,and impact sensitivity is H 50>125.9 cm.

关 键 词：不敏感增塑剂 偕二硝基 合成 性能 

分 类 号：TQ41[化学工程] TJ55[兵器科学与技术—军事化学与烟火技术]