磷溴阻燃环氧树脂的制备及应用
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摘要
以双酚A型环氧树脂(E-51)、四溴双酚A、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)或10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO-HQ)为原料,合成了2种磷溴阻燃环氧树脂(简称PB-1016、PBHQ-1016),然后与双酚A型酚醛树脂固化反应制备了覆铜板,采用红外光谱,凝胶渗透色谱,热重分析及阻燃性测试对磷溴阻燃环氧树脂和覆铜板进行了结构表征与性能研究。结果表明,磷溴阻燃环氧树脂具有明显的协同阻燃效应,并可提升含溴阻燃覆铜板的耐热性和相比漏电起痕指数(CTI)。PBHQ-1016具有良好的热稳定性,以其制备的覆铜板的阻燃性、耐热性、粘接性和CTI等性能表现较优,综合性能最佳。
The two kinds of phosphorous-bromine flame retardant epoxy resins(PB-1016 and PBHQ-1016)were synthesized by the reaction of epoxy resin(E-51),tetrabromobisphenol A and DOPO(or DOPO-HQ),then the copper clad laminates were prepared by the curing reaction of flame retardant epoxy resins and BPA novolac resin. The structure of the phosphorous-bromine flame retardant epoxy resins and the properties of the copper clad laminates were characterized and investigated by Infrared spectroscopy,gel permeation chromatography,thermogravimetric analysis and flame retardancy test. The results showed that the phosphorous-bromine flame retardant epoxy resin had obvious synergistic flame retardant effect,and it could improve the heat resistance and comparative tracking index(CTI) performance of Br flame retardant copper clad laminate. The PBHQ-1016 had good thermal stability,and its copper clad laminate had the best overall performance with excellent properties in flame retardancy,heat resistance,adhesion,CTI,etc..
The two kinds of phosphorous-bromine flame retardant epoxy resins(PB-1016 and PBHQ-1016)were synthesized by the reaction of epoxy resin(E-51),tetrabromobisphenol A and DOPO(or DOPO-HQ),then the copper clad laminates were prepared by the curing reaction of flame retardant epoxy resins and BPA novolac resin. The structure of the phosphorous-bromine flame retardant epoxy resins and the properties of the copper clad laminates were characterized and investigated by Infrared spectroscopy,gel permeation chromatography,thermogravimetric analysis and flame retardancy test. The results showed that the phosphorous-bromine flame retardant epoxy resin had obvious synergistic flame retardant effect,and it could improve the heat resistance and comparative tracking index(CTI) performance of Br flame retardant copper clad laminate. The PBHQ-1016 had good thermal stability,and its copper clad laminate had the best overall performance with excellent properties in flame retardancy,heat resistance,adhesion,CTI,etc..
引文
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[2]张超,谢洪德,何顺伦.高CTI阻燃增强PBT复合材料的制备[J].中国塑料,2009,23(8):22-26.
[3]杨兴钰,张丽萍,万石官.5,5-二甲基-1,3,2-二氧磷杂环己酰胺衍生物的合成及其应用研究[J].化学试剂,2005,27(3):158-160.
[4]Chang Z H,Guo F,Chen J F,et al.Synergistic flame retardant effects of nano-kaolin and nano-HAO on LDPE/EPDM composites[J].Polymer.Degradation and Stability Stab.,2007,92(7):1204-1212.
[5]Wang C S,Lin C H.Synthesis and properties of phosphorus containing advanced epoxy resins[J].Journal of Applied Polymer Science,2000,75(3):429-436.
[6]Lyons J W.The chemistry and uses of fire retardants[M].New York:Wiley-Interscience,1970:22.
[7]Yang C P,Lee T W.Synthesis and properties of 4-hydroxy-2,3,5,6-tetrabromobenzylphos-phonate and effects of their flame retardance on impact polystyrene[J].Journal of Applied Polymer Science,1986,32(1):3005-3025.
[8]Green J,Chung J.Flame-retarding poly(butylene tereththalate)-properties,processing characteristics,and rheology[J].Journal of Fire Sci.,1990,8(4):254.
[9]唐林生,郝秋芬,李莉,等.六苯氧基环三磷腈与四溴双酚A对聚丙烯的协同阻燃作用[J].塑料工业,2013,41(1):104-108.
[10]杨海燕,吴保朝,尹展翔,等.新型磷溴复合环氧树脂的合成研究[J].广州化工,2013,41(23):86-87,93.
[11]林伟,范华勇,徐莹.一种环氧树脂组合物及其应用:CN105273362[P].2016-01-27.
[12]卢林刚,周霞,赵敏,等.新型树状磷-溴协效阻燃剂1,3,5-三(5,5-二溴甲基-1,3-二氧杂己内磷酰氧基)苯的合成及其应用研[J].化学试剂,2008,30(10):721-724.
[13]Stepek J,Daousy H.Additives for plastics[M].New York:Sptinger-Verlay,1983:208.
[14]肖卫东,李建宗.溴磷阻燃剂对环氧树脂固化物阻燃耐热性的影响[J].高分子材料科学与工程,1992,8(3):89-93.
[15]方克洪.新型高CTI覆铜板的研制[C].第十六届中国覆铜板技术·市场研讨会论文集,2015:61-65.