磷杂菲三氮唑双基化合物高效阻燃环氧树脂  

Highly efficient flame-retardant epoxy resin with a novel compound containing phosphaphenanthrene and triazole groups

作　　者：王鹏[1] 刘家豪 WANG Peng;LIU Jiahao(College of Sericulture,Textile and Biomass Sciences,Southwest University,Chongqing 400715,China)

机构地区：[1]西南大学蚕桑纺织与生物质科学学院,重庆400715

出　　处：《复合材料学报》2021年第10期3281-3289,共9页Acta Materiae Compositae Sinica

基　　金：国家自然科学基金(21905233);中央高校基本科研业务费专项资金(XDJK2020C024)。

摘　　要：以对苯二甲醛、3,5-二氨基-1,2,4-三氮唑和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为原料合成了一种磷杂菲三氮唑双基化合物(DTZ),将其用于高效阻燃环氧树脂。利用FTIR、NMR、GPC和元素分析表征了其分子结构,采用TG和DSC研究了环氧固化物的热性能,利用极限氧指数、垂直燃烧、锥形量热、拉伸性能测试仪探究了环氧固化物的阻燃和力学性能,通过分析DTZ的热裂解行为、热氧化降解行为及炭层的形貌和结构研究了其阻燃机制。结果表明,DTZ的引入会降低环氧固化物的起始降解温度和玻璃化温度,但会提高其高温残炭率和拉伸强力。DTZ可显著提升环氧固化物的阻燃性能,当添加量为6wt%时,所得固化物的极限氧指数(LOI)值为33.5%,UL-94测试等级达到V-0级,热释放速率峰值和总热释放量分别降低21.8%和18.2%。DTZ可通过猝灭自由基、稀释可燃气体、促进基体成炭,在气相和凝聚相同时发挥阻燃作用。A novel compound with phosphaphenanthrene and triazole groups(DTZ) for highly efficient flame-retardant epoxy resin was synthesized with p-phthalaldehyde, 3,5-diamino-1,2,4-triazole and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO). Its chemical structure was characterized by FTIR, NMR, GPC and elemental analysis. The thermal properties of epoxy thermosets were investigated by TGA and DSC analyses. The flameretardant and mechanical properties were evaluated by limiting oxygen index, UL-94, cone calorimeter and tensile tests. Moreover, the flame-retardant mechanism of DTZ was particularly investigated by analyzing the pyrolysis and thermo-oxidative degradation behaviors, along with the morphology and structure of residual char of epoxy thermoset. It reveals that the incorporation of DTZ decreases the initial degradation temperature and glass transition temperature, while increases the char yield at elevated temperature and tensile strength for thermoset. DTZ remarkably improves the flame retardancy of epoxy thermoset. With the incorporation of 6 wt% DTZ, the modified epoxy thermoset achieves an limit oxygen index(LOI) value of 33.5% and passes UL-94 V-0 rating. Moreover, the peak heat release rate and total heat release in cone calorimetry test decrease by 21.8% and 18.2%, respectively. DTZ shows high flame-retardant activity not only by diluting combustible volatiles and quenching active radicals in the gas phase, but also by promoting the char formation in the condensed phase.

关 键 词：环氧树脂 磷杂菲 三氮唑 阻燃 机制 

分 类 号：TB332[一般工业技术—材料科学与工程] TQ323.5[化学工程—合成树脂塑料工业]