磷氮阻燃剂DOPO-AN的合成及其阻燃环氧研究

SYNTHESIS OF PHOSPHORUS-NITROGEN FLAME RETARDANT DOPOAN AND ITS FLAME RETARDANT MODIFIED EPOXY RESIN

以9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO),2-氨基蒽醌(AN)和多聚甲醛(POM)为原料,通过一锅法合成了一种新型磷氮阻燃剂2-(N,N-二(9,10-二氢-9-氧杂-10-磷杂菲-10基)甲基)氨基蒽醌(DOPO-AN)。利用核磁共振谱(1H-NMR、31P-NMR)、红外光谱(FTIR)对其分子结构进行表征,并将DOPO-AN用于阻燃改性环氧树脂(EP)。运用差示扫描量热法、万能力学试验机、氧指数仪、垂直燃烧仪分别研究了DOPO-AN/EP复合材料的力学性能、热稳定性、阻燃性能。结果表明,阻燃剂DOPO-AN能明显改善环氧树脂的阻燃性和热稳定性。当体系磷元素质量分数为0.67%时(DOPO-AN/EP-8%),800℃时残炭率由0.45%增加到7.9%;极限氧指数(LOI)随阻燃剂量的增加而增加,由纯环氧树脂的25.3%提高到30.1%,垂直燃烧UL94等级达到V-0级。力学性能结果表明,环氧树脂的拉伸强度由836 MPa增加至863 MPa,说明DOPO-AN的加入对EP的力学性能影响不大。

A novel flame retardant,2-(N,N-bis(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl)methyl)aminoanthraquinone(DOPO-AN),was synthesized by using 9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide(DOPO),2-aminoanthraquinone(AN),polyoxymethylene(POM)as the raw materials.Its structure was characterized by Fourier transform infrared spectroscopy(FTIR)and nuclear magnetic resonance spectroscopy(1H-NMR,31P-NMR),and then DOPO-AN was used as the flame retardant to modify epoxy resin(EP).The mechanical properties,thermal properties,flame retardant properties of DOPO-AN/EP composites were investigated respectively.The results showed that the flame retardancy and thermal properties of epoxy resin were obviously improved by DOPO-AN.When the mass fraction of phosphorus was 0.67 wt.%(DOPO-AN/EP-8%),the char yield of DOPO-AN/EP-8%was increased to 7.9%at 800℃.The oxygen index(LOI)increased from 25.3%to 30.1%with the increase of DOPO-AN;the vertical combustion grade UL94 reached V-0 level.The results of mechanical property showed that the tensile strength of epoxy resin increased from 836 MPa to 863 MPa,indicating that the mechanical properties of EP unacted on DOPO-AN loading.