10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-膦菲-10-氧化物的合成

以三氯化磷、邻苯基苯酚和对苯醌为主要原料,通过三步反应合成了含磷阻燃剂10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-膦菲-10-氧化物(ODOPB)。首先将酯化、酰基化、水解反应连续进行,得到了中间体2-(2-羟基苯基)苯基膦酸(HPPA),收率92.5%。然后HPPA分子内脱水成环反应得到9,10-二氢-9-氧杂-10-膦菲-10-氧化物(DOPO),收率93.2%。最后DOPO与对苯醌进行加成反应得到ODOPB,收率90.2%。三步合成总收率77.8%。HPPA的合成原料配比为n(三氯化磷)∶n(邻苯基苯酚)=1.3,以三氯化磷部分加入部分滴加的方式,且n(直接加入三氯化磷)∶n(滴加三氯化磷)=5.5,于150~200℃滴加反应。用红外光谱、元素分析、核磁氢谱、质谱对产物进行了表征。ODOPB已在覆铜板环氧树脂中成功应用,该合成方法已申请国家专利,正在进行产品中试。

Synthesis of 10- (2,5-dihydroxyphenyl) -9,10-dihydro- 9- oxa-10-phosphaphenanthrene-10-oxide

An organophosphorus flame retardant,10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(ODOPB) was synthesized from phosphorus trichloride,o-phenylphenol and p-benzoquinone through three-step process.Firstly the intermediate 2-(2-hydroxyphenyl)phenylphosphinic acid(HPPA) was prepared in 92.5% yield through continuous esterification,acylation and hydrolysis.Then through intermolecular dehydration-cyclization of HPPA,9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) was obtained in 93.2% yield.Lastly ODOPB was obtained in 90.2% yield from the addition reaction of DOPO and p-benzoquinone.The overall yield reached 77.8%.Reaction conditions for HPPA were as follows.n(PCl_3)∶n(o-phenylphenol)=1.3∶1.A part of PCl_3 was added at the beginning and the remainder(about 1/6.5 of total PCl_3) was dripped later at 150~200 ℃.The products were characterized by FTIR,elementary analysis,~1H NMR and MS.ODOPB has been used in epoxy resins of copper clad laminates successfully,and now is in pilot-scade experiment.The corresponding patent about the ODOPB synthesis was applied for.