端氨基环三聚磷腈在阻燃环氧树脂中的应用.doc

端氨基环三聚磷腈在阻燃环氧树脂中的应用 摘 要：利用亲核取代反应和非均相催化氢转移还原法合成了六对氨基苯氧基环三磷腈（HANPCP），并用核磁共振氢谱进行了表征。在环氧树脂EP)/间苯二胺体系中，加入HANPCP后可同时提高EP的力学性能和阻燃性能。在添加5份HANPCP时，与比空白样品相比，EP样品的拉伸强度提高了16.9%，冲击强度提高19.3%，垂直燃烧性能最优，达UL 94V1级。同时加入HANPCP后EP样品氧指数，在HANPCP10份时达到35.5%。热重红外联用仪及残炭SEM分析结果表明HANPCP的阻燃机理主要是捕捉环氧脱水产物生成较稳定物质，同时生成的磷酸催化EP分解形成致密，将难燃气体包裹在内部，阻止了氧气与EP进一步接触。 关键词：环氧树脂；六对氨基环三磷腈；阻燃；热分析 中图分类号：TQ323.5 文献标识码：A Application of Terminal Amino Phosphazene in Flame Retardant Epoxy Resin AbstractBy using the nucleophilic substitution reaction and heterogeneous catalytic hydrogen transfer reduction, the hexakis(p-aminophenoxy) cyclotriphosphazene (HANPCP) was prepared and characterized with NMR. The addition of HANPCP to epoxy composite (EP) contributed to the promotion in terms of both flame retardant and mechanical properties. When the additive amount of HANPCP was 5%, the vertical combustion performance of EP samples was optimal, which could reach to UL 94V-1 level and tensile and impact strength increased by 16.9% and 19.3% than that of neat EP, respectively. The OI increased with the addition of HANPCP into EP sample, it would reach to 35.5% when the content of HANPCP was 10 phr. The analysis results of TG-FTIR and SEM indicate that the flame retardant mechanism of HANPCP is mainly to capture the epoxy dehydration product to generate more stable material, phosphoric acid as catalyst and decomposition of EP generated form compact carbon layer, will be difficult to burn gas wrapped inside, preventing further contact with oxygen and EP. Key words: Epoxy resin; Hexakis(p-aminophenoxy) yclotriphosphazene; Flame retardancy; Thermal analysis 环氧树脂（EP）广泛应用于黏合剂、模塑材料、半导体灌封、涂料等行业，但纯EP属于易燃材料(LOI19)，因此对EP进行阻燃研究十分必要。传统卤系阻燃剂和氧化锑协同体系阻燃的环氧树脂体系在阻燃、绝缘、环境友好、力学性能等方面已无法满足要求。作为替代产品，磷系阻燃剂，具有阻燃效率高，阻燃环氧燃烧时生成较少腐蚀性有毒气体等优点[1]。 环三聚磷腈衍生物是一类骨架由磷和氮交替排列的无机-有机杂化化合物，具有分子表面能低、磷氮元素的协同阻燃、侧基的高反应活性、侧基被取代后的高耐热性等优点[2]，作为一种潜在高效无卤阻燃剂已被尝试应用于环氧树脂、ABS、聚碳酸酯(PC)等高分子基材中[3]。Gouri等[4]合成了六环氧丙醇基环三聚磷腈，以其为反应型阻燃剂，制备了阻燃环氧树脂；Liu等[5]合成了六对羟基苯氧基环三聚磷腈，制备了4种