新型环磷腈阻燃剂合成及其在环氧树脂中的应用

Synthesis and Performance in Epoxy Resins of Novel Cyclotriphosphazene Flame Retardants

以六氯环三磷腈、对羟基苯甲醛、三氯氧磷、新戊二醇等为原料,合成一种新型膨胀阻燃剂六(4(5,5-二甲基-1,3,2-二氧杂己内磷酰基)苯氧基)环三磷腈(HDDCPPCP)。通过红外光谱(FT-IR)、核磁氢谱(lH-NMR)及质谱(MS)对其结构进行表征。固定HDDCPPCP/聚磷酸铵(APP)组分在整个体系中的质量分数为30%,研究两者在不同配比下,对环氧树脂(EP)阻燃性能、热稳定性能和力学性能的影响。实验结果表明,EP4(10% HDDCPPCP/20% APP/EP)在HDDCPPCP/APP/EP体系中性能最佳,其氧指数为43.8%,UL-94防火等级可达V^0级;热重分析结果表明,EP4在550℃时,成炭率达到40.8%;在整个体系中EP4的热释放速率峰值、热释放速率均值、质量损失损率均值、一氧化碳释放速率均值以及总热释放量较纯EP(EP0)分别下降94%、95.8%、83.3%、66.7%、91.4%,其残炭量增加了2.9倍;拉伸强度、弯曲强度和冲击强度比EP0分别提高了46.8%、228.2%和12.5%;SEM电镜显示,EP4燃烧后形成致密、光滑、连续的蜂窝状炭层结构。

With hexachlorocyclotriphosphazene (HCCP),parahdroxy benzaldehyde,phosphorus oxychlo-ride,neopentyl glycol as raw materials to synthesis a new type of expansion flame retardant six(4-(5,5-dimethyl-1,3,2-dioxaphosphorinanyl- 2-oxy phosphoryl) phenoxy) cyclotr- iphosphazenene (HDDCPPCP).Through the method of infrared spectroscopy (FT -IR),nuclear magnetic hydrogen spectrum(^1H -NMR),mass spectrometry(MS),the molecular structure was characterized,the mass fraction of fixed HDDCPPCP/ammonium polyphosphate (APP) components in the whole system was 30%,and the effect of flame retardancy,thermal stability and mechanical properties of epoxy resin under different ratio of HDDCPPCP/APP were explored.The results showed that,EP4 (10% HDD CPPQP/20% APP/EP) had the optimum performance in HDDCPPCP/APP/EP system,with high oxygen index(43.8%),UL-94 fire rating up to FH-1 and V-0 level.Thermogravimetric analysis showed the char yield reached 40.8% at 550 centigrade.EP4 peak heat release rate,the mean heat release rate,the mean loss rate of mass loss,the mean rate of release of carbon monoxide and total heat release were the lowest among the whole system.Compared with pure EP (EP0),it decreased by 94%,95.8%,83.3%,66.7%,91.4%,while its carbon residue increased by 2.9 -fold.Compared with those of EP0,the tensile,bending and impact strengths of EP4 increase 46.8%,228.2% and 12.5%.SEM electron microscopy indicated that after burning,EP4 formed a dense,smooth and continuous carbon layer honeycomb structure.