相转移催化法合成pAMMO均聚物

以3-溴甲基-3′-甲基环氧丁烷(BrMMO)为单体,通过阳离子开环聚合合成了3-溴甲基-3′-甲基环氧丁烷均聚物(pBrMMO),然后用相转移催化法对pBrMMO进行大分子叠氮化反应,得到了含能粘合剂3-叠氮甲基-3′-甲基环氧丁烷均聚物(pAMMO)。探讨了聚合反应温度以及叠氮化反应时间的影响,确定了0℃进行聚合反应所得pBrMMO产率较高,分子量可控,分子量分布较窄;叠氮化反应30 h后可叠氮化完全。采用核磁共振(1H-NMR)进行了结构确认。同时,通过热重分析(TGA)和差示扫描量热法(DSC)对所得产物进行了表征。结果表明,pAMMO的热分解存在两个阶段,玻璃化转变温度为-44.54℃。

Synthesis of pAMMO Homopolymer by Phase Transfer Catalytic Method

3-bromomethyl-3′-methyloxetane homopolymer(pBrMMO) was synthesized using 3-bromomethyl-3′-methyloxetane(BrMMO) monomer by cationic ring opening polymerization at first,3-azidomethyl-3′-methyloxetane homopolymer(pAMMO) energetic binder was then synthesized through a phase transfer catalytic method.The effects of temperature on polymerization and reaction time on aziding were discussed emphatically.The results show that products with high yield,controllable molecular weight and narrow molecular distribution can be obtained when polymerization is carried out at 0 ℃.The optimal time of aziding is 30h.1H nuclear magnetic resonance spectrum(1H-NMR) was used to confirm the chemical structure of pAMMO.At the same time,the product is characterized by thermogravimetric analysis(TGA) and differential scanning calorimetry(DSC).The results show that there are two steps in the thermal decomposition of pAMMO and that the glass transition temperature of pAMMO is-44.54 ℃.