新型阻燃剂三笼状磷酰胺的合成及应用

Synthesis and Application of Novel Flame Retardant Tricyclic Caged-phosphoramide

为了提高不饱和聚酯树脂(UPR)的阻燃性能,设计合成了一种新型高效的阻燃剂膦酰三(N,N,N-甲基硅酸三羟甲基笼状酯)胺(PTSA)。通过实验优化了最佳反应条件:在氮气保护下,以二乙二醇二甲醚为溶剂,甲基硅酸三羟甲基甲胺笼状酯(TMCES)与三氯氧磷的物质的量之比为3.1∶1,在110℃下反应5 h,收率为81.4%,分解温度为271℃。利用傅立叶变换红外光谱、核磁共振氢谱确定了产物的化学结构。利用热重-差热分析、极限氧指数(LOI)、扫描电子显微镜等分析了产物的阻燃性能和灼烧残渣的微观形貌。结果表明,将PTSA与UPR复配后,PTSA质量分数为15%时,LOI达到28%,UL94等级可达到V–1级,属于难燃级别,硅/氮/磷三种阻燃元素有效发挥协同阻燃作用,显示出良好的协同阻燃效能。

In order to improve the flame retardancy of unsaturated polyester resin unsaturated polyester resin(UPR),a new and efficient flame retardant tris(N,N,N-methylsilicic acid trimethylolcaged ester)amine(PTSA)was designed and synthesized.The optimum reaction conditions were obtained by experiments:Under the protection of nitrogen,diethylene glycol dimethyl ether was used as solvent,n(trimethylolmethylamine clathrate of methylsilicate)∶n(phosphorus oxychloride)=3.1∶1,and reacted at 100℃for 5 h,the yield was 81.4%and the decomposition temperature was 271℃.The chemical structure of the product was analyzed by Fourier transform infrared reflection,1 H nuclear magnetic resonance,and the flame retardancy and micro morphology of burning residue of the product was analyzed by thermogravimetric analyzer,limiting oxygen index(LOI)and scanning electron microscope.The results show that after compounding PTSA and UPR,when the content of PTSA is 15%,the LOI reaches 28%,and the UL 94 grade can reach V–1,which belongs to flame retardant grade,silicon/nitrogen/phosphorus three flame retardant elements effectively plays a synergistic flame retardant effect and shows good synergistic flame retardant effect.