DOPO型环氧树脂用阻燃剂的合成与应用研究

Synthesis and Application of DOPO Type Flame Retardants for Epoxy Resin

摘要:

以对苯二胺、4-氟苯甲醛、4-硝基苯甲醛、4-甲氧基苯甲醛、9,10-二氢-9-氧-10-磷杂菲-10-氧化物（DOPO）为原料，经两步反应，合成了3种含磷、氮的DOPO型环氧树脂用阻燃剂，通过1H-NMR、FTIR对中间体及目标产物结构进行了表征。将合成的阻燃剂按0.00%、5.00%、10.00%、15.00%、20.00%加入到环氧树脂(EP)中，加入4, 4’-二氨基二苯基甲烷（DDM）固化后得到透明的复合材料，并对复合材料的热稳定性和阻燃性能进行了初步评价。结果表明：添加阻燃剂后的固化物初始失重温度高于300℃，可满足高分子材料加工时对热稳定性的要求；随着固化物中磷含量的增加，固化物的阻燃性增大；当固化物中磷含量达到1.00 w%时，所有固化物都可以达到UL94 V-0级，测得其中N,N’-双[4-硝基苯基]-1-(9-氢-9-氧杂-10-磷杂菲-10-氧化物)-甲基]-1,4-苯二胺BNP-DOPO/DDM/EP固化物的极限氧指数(LOI)值为37.0，是三组固化物中最高者。

Abstract:

Three phosphorus-nitrogen DOPO type flame retardants for epoxy resin were synthesized through two steps from p-phenylenediamine, 4-fluorobenzaldehyde, 4-nitrobenzaldehyde, 4-methoxybenzaldehyde and 9,10-dihydro-9-oxa-10-phosphoryl phenanthrene-10-oxide (DOPO). The intermediates and the target compounds were characterized by 1H NMR and FTIR. The obtained retardant and 4,4'-methylenedianiline were added to EP and transparent cured epoxy resin were obtained. The flame retardant performance of the cured products was investigated, respectively. The results indicated that with the increase of phosphorus content in the cured products, their flame-retardant performance increase. When the phosphorus content reached 1.00 w%, the cured EP can meet UL 94 V-0 class. The limiting oxygen index of BNP-DOPOD/DDM/EP was determined to be 37.0 as the highest among them.