六苯氧基环三磷腈的合成及其在层压板中的阻燃应用

Synthesis of Hexaphenoxycyclotriphosphazene and Its Application in Laminate

以六氯环三磷腈(HCCTP)粗产物、苯酚、NaOH为原料,四丁基氯化铵(TBAC)为相转移催化剂,氯苯和水为溶剂,合成了六苯氧基环三磷腈(HPCTP),考察了反应温度、反应时间、反应溶剂、物料配比对收率的影响。结果表明,在最佳原料配比n(NaOH)∶n(苯酚)∶n(TBAC)∶n(HCCTP粗产物)=7.5∶6.3∶0.15∶1、30℃反应4 h、回流反应6 h条件下,HPCTP的收率达到75%。采用红外光谱、核磁氢谱、碳谱、磷谱、X射线衍射分析、示差扫描量热分析、热重分析测试技术对产物进行了表征,并首次用于苯并噁嗪树脂玻璃布层压板,当HPCTP的质量分数为10%时,燃烧等级达到V-0级,平行击穿电压为47 kV,热态弯曲强度为596 MPa。

Hexaphenoxycyclotriphosphazene（HPCTP）was synthesized by the reaction of crude hexachloro-cyclotriphosphazene（HCCTP） with phenol and sodium hydroxide,with tetrabutylammonium chloride（TBAC） as phase transfer catalyst and chlorobenzene/water as solvent.Effects of reaction temperature,reaction time,solvent and molar ratio of raw matesials on the yield of HPCTP were investigated.Under the optimized reaction conditions of n（sodium hydroxide）∶n（phenol）∶n（TBAC）∶n（crude HCCTP）=7.5∶6.3∶0.15∶1,reaction time of 4 h at 30 ℃ plus 6 h at reflux temperature,the yield was 75%.The product was characterized by FTIR,1H NMR,13C NMR,31P NMR,XRD,DSC and TGA.The product has been firstly applied in benzoxazine resin glass cloth laminate.The flammability class of the laminate was in the rank of V-0,the breakdown voltage of the laminate was 47 kV,and the thermal state flexural strength of the laminate was 596 MPa when the mass fraction of HPCTP in the laminate was 10%.