DOPO改性氧化石墨烯阻燃环氧树脂研究
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摘要
采用9,10-二氢-9-氧杂-10-磷杂菲-10氧化合物(DOPO)对氧化石墨烯(GO)进行表面修饰,并制备阻燃环氧树脂(EP)复合材料。通过傅里叶红外光谱(FT-IR)、X射线衍射(XRD)及热失重分析(TGA)对改性氧化石墨烯(DOPO-GO)进行表征,采用锥形量热仪、扫描电子显微镜(SEM)等对EP复合材料的阻燃性能、残炭微观结构等进行研究。结果表明:DOPO成功对GO进行表面修饰,当DOPO-GO添加量为3%时,EP复合材料的残炭率比纯EP提高了1.8%,从而达到一定的阻燃效果。锥形量热仪测试及残炭微观结构观察得出,EP复合材料热释放速率峰值随着DOPO-GO添加量的增加而降低,接枝后的DOPO-GO会生成PO·,可以捕获聚合物燃烧后释放出的活性自由基H·和OH·,达到中断链式反应的效果。同时,加入DOPO-GO后,复合材料燃烧后的炭层致密,起到延缓环氧基体燃烧的作用。
9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) has been grafted onto the surface of graphene oxide(GO) and flame retardant epoxy resin(EP) composites were prepared by reacting epoxy ring groups together with the reduced graphene structure(DOPO-GO). Modified graphene oxide(DOPO-GO) was characterized by fourier transform infrared spectroscopy(FT-IR), X-ray diffraction(XRD) and thermogravimetric analysis(TGA). The flame retardancy and residual carbon microstructure of EP composites were studied by cone calorimeter and scanning electron microscopy(SEM). The results show that the surface modification of GO by DOPO is successful. When the DOPO-GO content is 3%, the residual carbon rate of EP composite increases by 1.8% compared with pure EP, thus achieving a certain flame retardant effect. The results of cone calorimeter test and observation of residual carbon microstructure show that the peak value of the heat release rate of the flame retardant epoxy composite material gradually decreases with the increase of the amount of DOPO-GO. The grafted DOPO-GO generates PO· which can capture radicals H· and OH· and achieve the effect of interrupting the chain reaction. At the same time, when DOPO-GO was added, the carbon layer of the composite was dense after combustion, which played a role in delaying the combustion of epoxy matrix.
9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) has been grafted onto the surface of graphene oxide(GO) and flame retardant epoxy resin(EP) composites were prepared by reacting epoxy ring groups together with the reduced graphene structure(DOPO-GO). Modified graphene oxide(DOPO-GO) was characterized by fourier transform infrared spectroscopy(FT-IR), X-ray diffraction(XRD) and thermogravimetric analysis(TGA). The flame retardancy and residual carbon microstructure of EP composites were studied by cone calorimeter and scanning electron microscopy(SEM). The results show that the surface modification of GO by DOPO is successful. When the DOPO-GO content is 3%, the residual carbon rate of EP composite increases by 1.8% compared with pure EP, thus achieving a certain flame retardant effect. The results of cone calorimeter test and observation of residual carbon microstructure show that the peak value of the heat release rate of the flame retardant epoxy composite material gradually decreases with the increase of the amount of DOPO-GO. The grafted DOPO-GO generates PO· which can capture radicals H· and OH· and achieve the effect of interrupting the chain reaction. At the same time, when DOPO-GO was added, the carbon layer of the composite was dense after combustion, which played a role in delaying the combustion of epoxy matrix.
引文
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[11]吴凡,陈东梁,张东胜,等.石墨烯接枝9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)的功能化合成[J].解放军理工大学学报,2013,5(14):545-549.
[12]Yuqiang Guo,Chenlu Bao,Lei Song,et al.In situ polymerization of graphene,graphite oxide,and functionalized graphite oxide into epoxy resin and comparison study of onthe-flame behavior[J].Industrial Engineering Chemistry Research,2011,50:7 772-7 783.
[13]Liu S,Fang Z P,Yan H Q,et al.Superior flame retardancy of epoxy resin by the combined addition of graphene nanosheets and DOPO[J].RSC Advances,2016,6:5 288-5 295.
[2]庞锦英,莫羡忠,刘钰馨,等.阻燃香蕉纤维增强环氧树脂复合材料的动态力学性能和热性能研究[J].塑料科技,2014,42(12):29-33.
[3]Lee C,Wei X,Kysar J W,et al.Measurements of the elastic properties and intrinsic strength of monolayer graphene[J].Science,2008,321:385-388.
[4]Stankovich S,Dikin D A,Dommett G H B,et al.Graphenebased composite materials[J].Nature,2006,442(7100):282-286.
[5]Ramanathan T,Abdala A A,Stankovich S,et al.Functionalized graphene sheets for polymer nanocomposites[J].Nature Nanotechnology,2008,3(6):327-331.
[6]李谷才,李桂林,刘小娟,等.DOPO型环氧树脂用阻燃剂的合成与应用[J].精细化工,2015,32(7):789-793.
[7]Khalifah A,Salmeia,Sabyasachi G.An overview of some recent advances in DOPO-derivatives:Chemistry and flame retardant applications[J].Polymer Degradation and Stability,2015(113):119-134.
[8]Artner J,Ciesielski M,Walter O,et al.A novel DOPO-based diamine as hardener and flame retardant for epoxy resin systems[J].Macromolecular Materials Engineering,DOI:10.1002/mame.200700287.
[9]吴传芳,李忠伦,陈文静,等.DOPO无卤阻燃环氧树脂体系的增韧改性研究[J].热固性树脂,2015,30(1):17-20.
[10]邹林,邹丽,刘晓波,等.阻燃剂DOPO及其衍生物在环氧树脂中的应用[J].热固性树脂,2014,29(4):55-65.
[11]吴凡,陈东梁,张东胜,等.石墨烯接枝9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)的功能化合成[J].解放军理工大学学报,2013,5(14):545-549.
[12]Yuqiang Guo,Chenlu Bao,Lei Song,et al.In situ polymerization of graphene,graphite oxide,and functionalized graphite oxide into epoxy resin and comparison study of onthe-flame behavior[J].Industrial Engineering Chemistry Research,2011,50:7 772-7 783.
[13]Liu S,Fang Z P,Yan H Q,et al.Superior flame retardancy of epoxy resin by the combined addition of graphene nanosheets and DOPO[J].RSC Advances,2016,6:5 288-5 295.