新型磷氮阻燃剂TGICA-DOPO的合成及其对乙烯基酯树脂阻燃性能的影响

Preparation of a novel flame retardant TGICA-DOPO and its effects on the properties of vinyl ester resin

以异氰尿酸三缩水甘油酯(TGIC)、丙烯酸和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为主要原料,合成了一种含P和N元素的新型阻燃添加剂TGICA-DOPO,将其应用在乙烯基酯树脂(VER)中可以制备具有良好阻燃性能的TGICA-DOPO/VER复合材料。通过FTIR光谱、核磁共振(31 P-NMR和1 H-NMR)等对TGICA-DOPO的分子结构进行了表征;通过极限氧指数(LOI)测试、TGA和DMA研究了TGICA-DOPO/VER树脂体系的阻燃性能和耐热性能。结果表明,当树脂体系中TGICA-DOPO的质量分数为30wt%时,LOI达到35;当体系中TGICA-DOPO的质量分数为25wt%时,树脂浇铸体在800℃下的残炭量提高了322%;FTIR和SEM测试结果表明,燃烧时TGICA-DOPO有助于形成高致密、连续炭层,隔绝了热量和空气向基材的传递,从而在凝聚相中发挥阻燃作用。

A novel flame retardant containing P and N was successfully synthesized via the addition reaction be- tween triglycidyl isocyanurate （TGIC）, acrylic acid and 9, 10-dihydro 9-oxa-10-phosphaphenanthrene-10 oxide （DOPO）. A flame retardant composite material TGICA-DOPO/vinyl ester resin （VER） was prepared by applying it to VER. The structure of TGICA-DOPO is characterized by FTIR, 1H and 31P nuclear magnetic resonance （NMR）. The flame retardancy and thermal properties of TGICA-DOPO/VER resin system were respectively inves- tigated by limited oxygen index （LOI） measurement, TGA and DMA. The results show that the LOI value of the resin system containing 30wt% TGICA-DOPO is improved to 35. TGA results indicate that the char yields of VER casting containing 25wt% TGICA-DOPO under 800℃ is increased by 322%. The FTIR and SEM results indicate that TGICA-DOPO promotes the formation of continuous, compact and intumescent char layer which can reduce the efficiency of heat- and oxygen-exchange.