自制高效无卤含磷阻燃剂阻燃环氧树脂研究

Study on Self⁃made High Efficiency Halogen⁃free Phosphorus⁃containing Flame⁃retardant Epoxy Resin

采用自制的阻燃剂双{4⁃[4⁃(4⁃氨基苄基)苯氨基][(6⁃氧二苯并[c,e][1,2]氧磷菲⁃6⁃基)甲基]苯基}苯基膦酸酯(DOP⁃DDM),以及DOP⁃DDM与金属氧化物复合,分别用于制备高效阻燃环氧树脂(EPM)。通过极限氧指数(LOI)、垂直燃烧(UL 94)和锥形量热燃烧试验评价了阻燃性能,利用热失重分析和动态热机械分析研究了热性能,热失重与红外光谱仪联用、扫描电子显微和拉曼光谱分析了阻燃机理。结果表明,DOP⁃DDM的引入会降低阻燃EPM的起始降解温度,但不会影响其玻璃化转变温度,提高了残炭率、储能模量、损耗模量和阻燃性能;DOP⁃DDM添加量为4.7%(质量分数,下同),磷含量仅0.37%,阻燃EPM的LOI值为33.5%,UL 94达V⁃0级,热释放速率峰值、总热释放量和总烟释放量分别降低了23.2%、17.8%和12.4%;3.7%的DOP⁃DDM与1.0%的Al2O_(3)复合,阻燃EPM达UL 94 V⁃0级,不仅热释放速率峰值和总烟释放量进一步降低,而且CO和CO_(2)毒气分别降低了7.7%和17.2%。

Highly efficient flame⁃retarded epoxy resin(EPM)was prepared by using a self⁃made flame retardant bis{4⁃[4⁃(4⁃aminobenzyl)phenylamino][(6⁃oxydibenzo[c,e][1,2]oxophenanthrene⁃6⁃yl)methyl]phenyl}phenyl phosphonate(DOP⁃DDM)compounding with metal oxide.The flame retardant performance of the resultant EPM was evaluated using limiting oxygen index(LOI),vertical combustion(UL 94)and cone calorimetric combustion test,and its thermal performance was investigated through thermogravimetry and dynamic thermal mechanical analyses.The flame retardant mechanism was analyzed by combining thermogravimetry analysis with infrared spectroscopy,scanning electron micros⁃copy and Raman spectroscopy.The results indicated that the introduction of DOP⁃DDM reduced the initial degradation temperature of the EPM without any effect on glass transition temperature and increased the residual char yield,storage modulus,loss modulus,and flame retardant properties.When 4.7 wt%of DOP⁃DDM was incorporated,the resultant EPM achieved a phosphorus content of only 0.37 wt%but a high LOI of 33.5%with a UL 94 classification of V⁃0.Its peak heat release rate,total heat release and total smoke release decreased by 23.2%,17.8%and 12.4%,respective⁃ly.When 3.7 wt%DOP⁃DDM was combined with 1.0 wt%Al2O_(3),the EPM exhibited a reduction not only in peak heat release rate and total smoke emission but also in CO and CO_(2) toxic gases by 7.7%and 17.2%,respectively.