环三磷腈基多官能液体环氧树脂(HGCP)的合成与热性能

以六氯环三磷腈、2,3-环氧基-1-丙醇为原料,得到六缩水甘油基环三磷腈(HGCP)。通过红外、核磁、质谱及元素分析对产物结构进行了表征,并研究了溶剂、原料配比、反应温度和时间对反应的影响。结果表明,合成的最佳条件是:四氢呋喃为溶剂,反应物料配比为n(2,3-环氧基-1-丙醇):n(六氯环三磷腈)=7.62,反应温度为30℃,反应时间4.0 h,产品收率达到78%。选取顺丁烯二酸酐(MA)和4,4-二氨基-二苯-甲烷(MDA)为固化剂,通过热失重分析和线烧蚀率研究了不同固化体系的耐热性和耐烧蚀性。研究表明,六缩水甘油基环三磷腈表现出优良的热稳定性,其交联产物EPG-1和EPG-2在高温条件下残炭量较高,线烧蚀率分别为0.344 mm/s和0.364 mm/s,可作为固体火箭推进剂绝热包覆材料使用。

Synthesis, characterization and thermal property of hexaglycidylcyclotriphosphazene (HGCP)

Hexaglycidylcyclotriphosphazene(HGCP) was prepared from hexachlorocyclotriphosphzene and 2,3-epoxy-1-propanol.The products was structurally characterized by FT-IR,1H,31P,13C NMR spectroscopy and elemental analysis.The factors affecting the yield of HGCP,such as reagent,ratio of 2,3-epoxy-1-propanol /hexacholrocyclotriphosphazene(P),reaction temperature(T) and time(t) were investigated.The optimized process conditions were: 2,3-epoxy-1-propanol/hexacholrocyclotriphosphazene(P)=7.62,T=30 ℃ and t=4.0 h with tetrahydrofuran as solvent.The yield and purity of the resulting HGCP could be up to 78%.Results show that the HGCP exhibits prefect heat-resistance and flame retardant resistance,and the linear ablation rate of cross-linking products EPG-1 and EPG-2 could up to 0.344 mm/s and 0.364 mm/s,so it is suitable to be used as organic filler in insulation layer for the solid rocket motor.