无卤反应型含磷氮阻燃剂的合成及其阻燃改性环氧树脂的研究
邵志恒,李纪录,陈显明,许一婷,罗伟昂,陈国荣,曾碧榕,袁丛辉,戴李宗*

(厦门大学 材料学院,福建省防火阻燃材料重点实验室,福建 厦门 361005)

环氧树脂; 磷氮阻燃剂; 席夫碱基化合物; 反应型

Synthesis of Halogen-free Reactive Flame Retardants Containing P-N and Investigation of Flame-retarded Modification on Epoxy Resin
SHAO Zhiheng,LI Jilu,CHEN Xianming,XU Yiting,LUO Wei'ang,

(Key Laboratory of Fire Retardant Materials of Fujian Province,College of Materials,Xiamen University,Xiamen 361005,China)

epoxy resin; P-N flame retardant; Schiff-base compound; reactive

DOI: 10.6043/j.issn.0438-0479.201703025

备注

通过N-羟乙基苯胺、4-羟基苯甲醛、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)反应,合成了一种反应型含磷氮阻燃剂6-((4-((2-羟乙基)氨基)苯基)(4-羟基苯基)甲基)二苯并-[1,2]-氧磷腈-6-氧化物(PNOH).以PNOH为阻燃剂与4,4'-二氨基二苯甲烷复配制得了阻燃环氧树脂PNOH/EP,并研究了PNOH添加量(质量分数)对PNOH/EP各项性能的影响.结果表明,PNOH/EP的热稳定性较好,其热分解残炭率较纯的环氧树脂有明显提高; 当PNOH添加量为2.4%时,PNOH/EP的极限氧指数(LOI)大于30.0%,垂直燃烧等级为V-0级,储能模量及热稳定性有所提高; 当PNOH添加量为10.0%时,PNOH/EP的LOI达到36.0%.阻燃剂PNOH含磷、氮元素,可起到无卤协同阻燃的作用,其与环氧树脂反应生成的复合材料能保持基体良好的热性能和机械性能.

In this study,the reactive flame retardant called 6-((4-((2-hydroxyethyl)amino)phenyl)(4-hydroxyphenyl)methyl)dibenzo-[1,2]-oxaphosphinine 6-oxide(PNOH),containing P and N elements,was synthesized via the reaction between N-phenyldiethanolamine,4-hydroxybenzaldehyde and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO).PNOH was then incorporated into epoxy resin to prepare the flame retardant epoxy resin PNOH/EP,and the effects of the additive amount of PNOH on the properties of PNOH/EP were studied using different testing methods.The results showed that PNOH/EP cured compounds,of which the char residue was higher than pure epoxy resin,had better thermal stability.When the additive amount of PNOH was 2.4%,the limit oxygen index(LOI)of PNOH/EP was more than 30.0%,the vertical combustion grade was V-0,and the storage modulus and thermal stability were improved.When the additive amount of PNOH was 10.0%,the LOI of PNOH/EP reached 36.0%.The flame retardant containing P and N elements could have a halogen-free synergistic flame retardancy effect,keeping good thermal and mechanical performance of PNOH/EP cured compounds simultaneously.