端羟基叠氮呋咱醚氧杂丁烷-HTPE嵌段共聚物合成及内增塑性能  

Synthesis and Internal Plasticization of(Azidofurazan-ether based Oxetane)-HTPE Copolymer

作　　者：温昱佳 张婧 窦金康 谭博军 刘宁[1,2] WEN Yu-jia;ZHANG Jing;DOU Jin-kang;TAN Bo-jun;LIU Ning(Xi′an Modern Chemistry Research Institute,Xi′an 710065,China;State Key Laboratory of Fluorine&Nitrogen Chemicals,Xi′an 710065,China)

机构地区：[1]西安近代化学研究所,陕西西安710065 [2]氟氮化工资源高效开发与利用国家重点实验室,陕西西安710065

出　　处：《含能材料》2024年第6期651-659,I0003,共10页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金(22175139,22105156)。

摘　　要：针对增塑剂易迁移、渗出进而严重影响聚合物基复合材料物化性能和机械性能的问题,研究通过3-硝基-4-羟基呋咱与3,3-二溴甲基氧杂丁环(BBMO)偶联合成2种新单体3-(4-硝基呋咱-3-氧甲基)-3-溴甲基氧杂环丁烷(BrNFMO)、3,3-二(4-硝基呋咱-3-氧甲基)氧杂环丁烷(BNFMO),以端羟基聚醚(HTPE)为大分子引发剂,在三氟化硼乙醚催化下分别与BrNFMO、BNFMO以及对照组BBMO共聚后叠氮化,制备得到三种内增塑嵌段共聚物,对其进行结构、热分解行为、内增塑性能测试,并对所设计目标共聚单元进行量化计算以评估其爆轰性能。最后对共聚工艺进行了优化,通过“假活性”聚合策略对引入嵌段的程度进行控制。结果表明,该系列新型含能共聚单元具有优于现有叠氮基氧杂环丁烷单体的能量水平。与直接将叠氮基团引入聚合物相比,通过呋咱醚桥联结构将叠氮基团进行引入能够通过内增塑策略获得具有更低玻璃化转变温度T_(g)与黏度的含能共聚物(T_(g)可降低5.27℃,黏度可降低4.90 Pa·s),其热稳定性也得到了提高(T_(d)可提高7.3℃)。Migration and leaching of plasticizers will severely affect the physical and mechanical properties of polymers.In this study,two new monomers,3-(4-nitrofurazan-3-oxy-methyl)-3-bromomethyl oxetane(BrNFMO)and 3,3-bis(4-nitrofurazan-3-oxy-methyl)oxetane(BNFMO),were synthesized by the combination of 3-nitro-4-hydroxy-furazan and dibromomethyl oxetane(BBMO).Using hydroxy-terminated polyether(HTPE)as macromolecular initiator,three block copolymers containing azide groups were synthesizd by polymerization of BrNFMO,BNFMO and BBMO under the catalysis of boron trifluoride ether followed by azidation process.Then the detonation performance of the designed monomer structure was evaluated by quantum chemistry.Besides,the copolymerization process was optimized by the control variate method,and better copolymerization conditions were obtained.The results show that this series of novel energetic copolymers can further improve the energy level of the binders,and the intramolecular plasticizing strategy can result in energetic polymers with lower glass transition temperature(T_(g))and viscosity by introducing azide groups into the polymer through the structure of azidofurazan ether,compared with directly introducing azide groups into the polymer.T_(g) can be reduced by 5.27℃,viscosity can be reduced by 4.90 Pa·s,and its thermal stability is also improved(thermal decomposition temperature(T_(d))can be increased by 7.3℃).

关 键 词：呋咱含能聚合物 阳离子开环聚合 含能粘合剂 热稳定性 内增塑 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] TQ226[化学工程—有机化工]