含有氨基甲酸酯单元结构的端叠氮基环氧乙烷-四氢呋喃无规共聚醚的合成及表征  

Synthesis and Characterization of Azide Terminated Ethylene Oxide-tetrahydrofuran Copolyether

作　　者：张倩[1] 莫洪昌[1] 徐明辉[1] 陈曼[1] 卢先明[1] 刘宁[1] ZHANG Qian;MO Hong-chang;XU Ming-hui;CHEN Man;LU Xian-ming;LIU Ning(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：《火炸药学报》2020年第6期657-661,共5页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.21703168)。

摘　　要：为了解决端羟基环氧乙烷-四氢呋喃无规共聚醚黏合剂的固化过程水敏感问题,以端羟基环氧乙烷-四氢呋喃无规共聚醚(PET)为母体聚合物,首先与2-氯乙基异氰酸酯经过亲核加成反应制备出一种含氨基甲酸酯基团的端氯基共聚醚中间体(ClTUPET),再通过与叠氮化钠的亲核取代反应制备得到了含有氨基甲酸酯结构单元的端叠氮基四氢呋喃-环氧乙烷无规共聚醚(ATUPET),探讨了ATUPET的合成机理;采用红外光谱、核磁共振碳谱、凝胶渗透色谱、DSC以及TGA对产物的结构和性能进行了表征。结果表明,端位羟基转化完全,成功制备出了ATUPET,该合成方法简单,收率93.98%;ATUPET的玻璃化转变温度-69.4℃,冷结晶温度-47.2℃,熔点约为-8.6℃,热分解温度大于200℃,具有良好的热稳定性。The azide terminated ethylene oxide-tetrahydrofuran copolyether with urethane segments(ATUPET)was designed to solve its sensitivity to humidity during the curing process.It was prepared by a two-step method.Firstly,chloro terminated ethylene oxide-tetrahydrofuran copolyether with urethane segments(ClTUPET)was synthesized by nucleophilic addition between hydroxyl terminated ethylene oxide-tetrahydrofuran copolyether(PET)and 2-chloroethyl isocyanate.Then ATUPET was synthesized by nucleophilic substitution of ClTUPET with sodium azide.The product was characterized by IR,13C NMR,GPC,and DSC.The results indicate that the hydroxyl group disappears after modification with high yield of 93.98%.Meanwhile,the glass transition temperature of ATUPET is-69.4℃.Its cold crystallization temperature and melting temperature are-47.2℃and-8.6℃,respectively.The thermal decomposition temperature of ATUPET is more than 200℃,showing that ATUPET has a satisfactory thermal stability.

关 键 词：有机化学 端叠氮基 氨基甲酸酯 端羟基环氧乙烷-四氢呋喃无规共聚醚 PET 2-氯乙基异氰酸酯 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O62[理学—有机化学]