磷酰胺类阻燃剂的合成及在硬质聚氨酯泡沫塑料中的应用

Synthesis of Phosphoramidates Flame Retardant and Its Application in Rigid Polyurethane Foam

以亚磷酸二甲酯、二乙胺、正丁胺、环己胺为原料合成3种磷酰胺类阻燃剂二甲基-N,N-二乙基磷酰胺(DMDEPR)、二甲基-N-丁基膦酰胺(DMBPR)和二甲基-N-环己基磷酰胺(DMCHPR),用红外光谱仪、核磁共振仪、质谱仪和热重分析仪对其进行表征并研究了3种不同结构的磷酰胺类阻燃剂对硬质聚氨酯泡沫塑料(RPUF)阻燃性能的影响。结果表明,3种磷酰胺类阻燃剂和RPUF相容性较好,对RPUF力学性能影响不大。磷酰胺类阻燃剂的添加均使RPUF的阻燃性能有所提高,其中具有叔酰胺结构的DMDEPR阻燃效果最好,DMDEPR阻燃的RPUF热稳定性最高,添加10phr DMDEPR的RPUF其残炭量从空白RPUF的16.0%上升到25.2%。

Dimethyl-N,N-diethylphosphoramidate（ DMDEPR）,dimethyl-N-butylphosphoramidate（ DMBPR） and dimethyl-N-cyclohexylphosphoramidate（ DMCHPR） were prepared by reacting dimethyl phosphite and carbon tetrachloride with diethylamine,n-butylamine and cyclohexylamine respectively. Their structures were characterized by FT-IR,1H-NMR,mass spectrometer（ MS） and TGA. Effects of different structure-flame-retardant relationships of phosphoramidates on rigid polyurethane foam（ RPUF） were investigated. The results show that three kinds of phosphoramidates exhibit better compatibility with RPUF and lesser negative influence on mechanical properties of modified RPUF. All of them improve the flame retardancy of RPUF. Within the phosphoramidates,DMDEPR with a structure of tertiary amide exhibits the highest level of flame retardancy. DMDEPR-RPUF has the highest level of thermal stability. When the content of DMDEPR is 10 phr,the residual mass of DMDEPR-RPUF increases from 16. 0%（ for pure RPUF） to 25. 2%.