DOPO基阻燃环氧树脂便捷合成及相关性能  

Facile synthesis of DOPO based flame retardant epoxy resins and their related properties

作　　者：谢聪[1,2] 陈涛[1] 王奕[1] 朱梦娇 XIE Cong;CHEN Tao;WANG Yi;ZHU Mengjiao(Non-Power Nuclear Technology Research and Development Center,Hubei University of Science and Technology,Xianning,Hubei 437100,China;College of Materials,Xiamen University,Xiamen,Fujian 361005,China)

机构地区：[1]湖北科技学院非动力核技术研发中心,湖北咸宁437100 [2]厦门大学材料学院,福建厦门361005

出　　处：《中国科技论文》2019年第12期1283-1288,共6页China Sciencepaper

基　　金：湖北省自然科学基金资助项目(2019CFB239);湖北省教育厅科学研究计划项目(Q20172801);湖北科技学院2017年度校内科研发展基金资助项目(2018-19KZ06)

摘　　要：为永久高效提升环氧树脂阻燃性能,便捷合成了1,3-苯基-二(9,10-二氢-9-氧杂-10-磷杂菲基)二甲醇(1,3-phenyl-bis(9,10-dihydro-9-oxa-10-phosphaphenanyl)dimethanol,DOPO-1)和1,4-苯基-二(9,10-二氢-9-氧杂-10-磷杂菲基)二甲醇(1,4-phenyl-bis(9,10-dihydro-9-oxa-10-phosphaphenanyl)dimethanol,DOPO-2)2种反应型阻燃剂。它们与4,4′-二氨基二苯甲烷(4,4′-diaminodiphenylmethane,DDM)复配,再与等当量环氧树脂(E51)固化,制备了不同磷含量的DOPO基阻燃环氧体系。通过核磁共振(nuclear magnetic resonance,NMR)表征了DOPO-1和DOPO-2的结构,借助傅里叶变换红外光谱(Fourier transform infrared spectrometer,FTIR)跟踪固化历程,最后通过动态力学热分析(dynamic mechanical thermal analysis,DMTA)、热重分析(thermogravimetric analyzer,TGA)、氧指数(limiting oxygen index,LOI)测定和垂直燃烧测试(vertical combustion test,UL-94)研究了DOPO-1基和DOPO-2基阻燃环氧树脂热力学、耐热、阻燃性能与环氧体系磷质量分数、阻燃剂结构之间的关系。结果表明:1)DOPO-1/DDM和DOPO-2/DDM与E51固化后形成均相阻燃体系;2)随着磷质量分数的增加,DOPO-1基和DOPO-2基环氧树脂在700℃残炭率得到提高;3)磷的质量分数为1.0%时,环氧树脂均能达到阻燃等级UL94-V0级,磷的质量分数为1.7%就能使DOPO-1基和DOPO-2基环氧树脂LOI值分别达到40.9和41.9,且在环氧树脂阻燃性能发挥上,DOPO-2比DOPO-1更强。In order to improve flame retardant properties of epoxy resins efficiently and permanently, two kinds of reactive flame retardants, namely 1,3-phenyl-bis(9,10-dihydro-9-oxa-10-phosphaphenanyl)dimethanol(DOPO-1) and 1,4-phenyl-bis(9,10-dihydro-9-oxa-10-phosphaphenanyl)dimethanol(DOPO-2), were synthesized by a facile method. They were combined with 4,4′-diaminodiphenylmethane(DDM) and cured with the equivalent epoxy resins(E51). Finally, DOPO based flame retardant epoxy systems with different phosphorus contents were obtained. The structure of DOPO-1 and DOPO-2 was characterized by nuclear magnetic resonance(NMR), and the curing process was tracked by Fourier transform infrared spectrometer(FTIR). Subsequently, the relationship between thermodynamics, heat resistance, flame retardancy of DOPO-1/DOPO-2 based flame retardant epoxy resins and the mass fraction of phosphorus in epoxy systems, the structure of flame retardants were studied by dynamic mechanical thermal analysis(DMTA), thermogravimetric analyzer(TGA), limiting oxygen index(LOI) and vertical combustion test(UL-94) tests, respectively. The results show that a serials of homogeneous flame retardant systems are formed after curing reaction between DOPO-1/DDM & DOPO-2/DDM and E51. With the increase of phosphorus content, the carbon residue of DOPO-1 and DOPO-2 based epoxy resin increases at 700 ℃. When the phosphorus content is 1.0%, the epoxy resin can reach the flame retardant UL94-V0 level. When the phosphorus content is 1.7%, the LOI value of DOPO-1 and DOPO-2 based epoxy resin can reach 40.9 and 41.9, respectively. In addition, DOPO-2 is stronger than DOPO-1 in the performance of flame retardancy of epoxy resin.

关 键 词：功能高分子 反应型阻燃 DOPO衍生物 便捷合成 环氧树脂 阻燃性能 

分 类 号：TQ314.2[化学工程—高聚物工业]