化工新型材料

化工新型材料 ›› 2018, Vol. 46 ›› Issue (12) : 68-71.

新材料与新技术

磷氮阻燃剂PDAB-DOPO的制备及阻燃环氧树脂复合材料性能研究

作者信息 +

Preparation of phosphorus-nitrogen PDAB-DOPO and its flame retardant epoxy resin

Wang Zhiguo, Liang Bing, Liu Xuyue

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文章历史 +

Received
2017-08-04
Issue Date	Revised Date
2019-01-07	2017-08-04

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摘要

以对苯二胺、9,10-2H-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、四氯化碳为原料制备磷氮阻燃剂6,6′-(1,4-亚苯基双(氮烷二基)双(6H-二苯并[c,e][1,2]氧杂磷苯-6-氧化物)(PDAB-DOPO)。利用傅里叶变换红外光谱仪、核磁共振氢谱仪对PDAB-DOPO结构进行了表征并将其用于阻燃环氧树脂;通过热失重分析对PDAB-DOPO及环氧树脂复合材料的热性能进行了表征,通过极限氧指数(LOI)和UL94测试对环氧树脂复合材料阻燃性能进行了表征,通过扫描电子显微镜对环氧树脂复合材料残炭形貌进行了分析。结果表明:当体系中磷质量分数为1.65%时,800℃时环氧树脂复合材料残炭量提高到18.9%,环氧树脂复合材料体系的LOI为27.3%,通过UL 94 V-0级测试。扫描电子显微镜分析表明,PDAB-DOPO的加入使得环氧树脂体系残炭表面形貌发生明显变化,PDAB-DOPO对环氧树脂具有良好的阻燃效果。

Abstract

The phosphorus-nitrogen flame retardant 6,6′-(p-phenylenediamine-1,4-diyl) bis (6H-dibenzo [c,e] [1,2] oxophosphate-6-oxide) (PDAB-DOPO) was synthesized using p-phenylenediamine,9,10-2H-9-oxa-10-phospaphenanthrene-10-oxide (DOPO) and carbon tetrachloride as raw materials.The structure was characterized using FT-IR and ¹H-NMR,and the flame retard epoxy resin (EP) was prepared using PDAB-DOPO as flame retardant.The thermal properties of PDAB-DOPO and cured products were investigated by TGA,flame retardant properties was characterized by limit oxygen index (LOI) and vertical burning test (UL 94),and the residual carbon morphology was investigated by SEM.TGA results indicated that when the phosphorus content reached 1.65% in the EP system,the carbon residue rate can reached 18.9% at 800℃.LOI reached 27.3%,UL 94 passed V-0 level.And SEM results revealed that the addition of PDAB-DOPO can obviously improve the carbon residue morphology after combustion,and PDAB-DOPO can enhance the flame retardant properties of epoxy resin.

关键词

环氧树脂 / 阻燃 / 磷氮阻燃剂 / 复合材料 / 热性能

Key words

epoxy resin / flame retard / phosphorus nitrogen flame retardant / composite / thermal property

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磷氮阻燃剂PDAB-DOPO的制备及阻燃环氧树脂复合材料性能研究[J]. 化工新型材料, 2018, 46(12): 68-71 DOI:

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参考文献

原文顺序 | 出版日期 | 本文引用

[1] Jiao C M,Dong J,Zhang C J,et al.Synthesis and properties of a phosphate ester as curing agent in an epoxy resin system[J].Iran Polym J,2014,23(8):591-598.
[2] Ma S Q,Liu X Q,Jiang Y H,et al.Synthesis and properties of phosphorus-containing bio-based epoxy resin from itaconicacid[J].Sci China Chem,2014,57(3):379-388.
[3] Liang B,Wang G,Hong X D,et al.Synthesis and properties of a new halogen-free flame-retardant epoxy resin curing agent[J].High Perform Polym,2016,28(1):110-118.
[4] 韩明轩,许苗军,李斌.新型含磷阻燃剂DOPO-PPO的合成及其阻燃性能[J].合成化学,2016,24(2):98-101.
[5] 彭淑萍,陶纯初,卢鑫,等.新型含氮阻燃剂的合成与阻燃性能初探[J].塑料工业,2008,36(5):67-69.
[6] 单佳丽,宋荣君,李斌.一种新型含硅阻燃剂的制备及在聚碳酸酯中的应用研究[J].塑料科技,2016,44(4):90-94.
[7] Li Z S,Song T,Liu J G,et al.Thermal and combustion beha-vior of phosphorus-nitrogen and phosphorus-silicon retarded epoxy[J].Iran Polym J,2017,26(1):21-30.
[8] Wirasaputra A,Yao X H,Zhu Y M,et al.Flame-retarded epoxy resins with a curing agent of DOPO-triazine based anhydride[J].Macromol Mater Eng,2016,301(8):982-991.
[9] Min Y,Li P,Yin X G,et al.Synthesis and characterization of an novel flame retardant based on phosphaphenanthrene for epoxy resin[J].Polym Bull,2017,74(1):1-10.
[10] Wang P,Cai Z S.Highly efficient flame-retardant epoxy resin with a novel DOPO-based triazole compound:thermal stability,flame retardancy and mechanism[J].Polymer Degradation and Stability,2017,137:138-150.
[11] 辛梅华,郑德志,李明春,等.磷酰胺类阻燃剂的合成及在硬质聚氨酯泡沫塑料中的应用[J].高分子材料科学与工程,2016,32(1):19-24.
[12] Zhang Y,Yu B,Wang B B,et al.Highly effective P-P synergy of a novel DOPO-based flame retardant for epoxy resin[J].Ind Eng Chem Res,2017,56(5):1245-1255.
[13] Neisius N,Lutz M,Rentsch D,et al.Synthesis of DOPO-based phosphonamidates and their thermal properties[J].Ind Eng Chem Res,2014,53(8):2889-2896.
[14] Wang P,Yang F S,Li L,et al.Flame retardancy and mechanical properties of epoxy thermosets modified with a novel DOPO-based oligomer[J].Polymer Degradation and Stability,2016,129:156-167.
[15] Xie C,Du J F,Dong Z,et al.Improving thermal and flame-retardant properties of epoxy resins by a new imine linkage phosphorous-containing curing agent[J].Polym Eng Sci,2016,56(4):441-447.
[16] Luo C Y,Zuo J D,Wang F Q,et al.High refractive index and flame retardancy of epoxy thermoset cured by tris (2-mercaptoethyl) phosphate[J].Polymer Degradation and Stability,2016,129:7-11.
[17] Luo Q Q,Yuan Y C,Dong C L,et al.Intumescent flame retardancy of a DGEBA epoxy resin based on 5,10-dihydro-phenophosphazine-10-oxide[J].RSC Adv,2015,5(84):68476-68484.
[18] Wang Z G,Liang B.Synthesis of a new phosphorus-nitrogen flame retardant GAP-DOPO and its flame retardant perfor-mance for epoxy resin[J].2017,34(7):382-388.
[19] Xie C,Zeng B R,Gao H,et al.Improving thermal and flame-retardant properties of epoxy resins by a novel reactive phosphorous-containing curing agent[J].Polymer Engineering and Science,2014,54(5):1192-1200.