College of Materials Science and Engineering, Chongqing University, 174 Shazhengjie, Chongqing 400044, PR China.
College of Materials Science and Engineering, Chongqing University, 174 Shazhengjie, Chongqing 400044, PR China; Chongqing Key Laboratory of New Building Materials and Engineering, Chongqing University, 174 Shazhengjie, Chongqing 400044, PR China.
J Hazard Mater. 2019 Nov 5;379:120793. doi: 10.1016/j.jhazmat.2019.120793. Epub 2019 Jun 19.
In this study, a novel hyperbranched phosphorus/nitrogen-containing flame retardant (HPNFR) was facilely synthesized via the transesterification reaction of dimethyl methylphosphonate and tris (2-hydroxyethyl) isocyanurate and characterized successfully by H NMR and FTIR. The sample with 4 wt% HPNFR can achieve V-0 rating in UL-94 test and possess a LOI value as high as 34.5%. Conspicuous blowing-out effect was observed during the vertical burning test. TG results indicated that the presence of HPNFR significantly improved the thermal stability of EP thermosets. From cone test, THR, p-HRR, p-SPR and TSP values of HPNFR/EP composites were decreased in comparison to those of pure EP, revealing the reduced fire hazard of EP composites with HPNFR. SEM images of EP thermoset with 4 wt% of HPNFR after cone test exhibited compact and continuous char layers, while those of pure EP are fragmentary and broken. From TG-IR test, the yield of toxic CO and other pyrolysis products was significantly reduced, indicating a decrease in toxicity. Phosphorus-containing compounds were detected in gas phase, which verified the gaseous phase flame retardant effect of HPNFR. Besides, HPNFR would not significantly damage the transparence of EP thermosets, consequently reserved it's application value in some special fields.
在这项研究中,通过亚磷酸二甲酯和三(2-羟乙基)异氰尿酸酯的酯交换反应,简便地合成了一种新型的支化磷/含氮阻燃剂(HPNFR),并通过 H NMR 和 FTIR 成功进行了表征。在 UL-94 测试中,含 4wt% HPNFR 的样品可达到 V-0 等级,且 LOI 值高达 34.5%。在垂直燃烧测试中观察到明显的吹熄效应。TG 结果表明,HPNFR 的存在显著提高了 EP 热固性树脂的热稳定性。从锥形量热计测试结果来看,与纯 EP 相比,HPNFR/EP 复合材料的 THR、p-HRR、p-SPR 和 TSP 值降低,表明 HPNFR 降低了 EP 复合材料的火灾危险性。添加了 4wt% HPNFR 的 EP 热固性树脂在锥形量热计测试后的 SEM 图像显示出紧密连续的炭层,而纯 EP 的则是碎片状和破裂的。从 TG-IR 测试结果来看,有毒 CO 和其他热解产物的产率显著降低,表明毒性降低。气相中检测到含磷化合物,验证了 HPNFR 的气相阻燃效果。此外,HPNFR 不会显著损害 EP 热固性树脂的透明度,因此保留了其在某些特殊领域的应用价值。