4种PEPA衍生物阻燃剂的合成  

Synthesis of Four PEPA Derivatives as Flame Retardant

作　　者：房晓敏[1] 欧育湘[1] 

机构地区：[1]北京理工大学国家专业阻燃材料实验室

出　　处：《精细化工》2007年第4期401-403,412,共4页Fine Chemicals

摘　　要：1-氧基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷(PEPA)与三氯氧磷分别以摩尔比2∶1和3∶1反应,得到二(2,6,7-三氧杂-1-氧基磷杂双环[2.2.2]辛烷-4-亚甲基)磷酰氯(中间体Ⅰ)和三(2,6,7-三氧杂-1-氧基磷杂双环[2.2.2]辛烷-4-亚甲基)磷酸酯(d),产率分别为84.7%和80%。中间体Ⅰ再分别与三溴苯酚、五溴苄基溴及三聚氰胺反应得到另外3种具有笼状结构的磷酸酯化合物(a^c),收率依次为70%,73.5%,81%。用红外、核磁、元素分析等手段对a^d 4种化合物进行了表征,对其合成工艺进行了探讨。热失重数据表明,目标产物均有较好的成炭性和热稳定性,化合物a^d的初始热分解温度分别为285,325,320,337,500℃时残炭质量分数分别达38.4%,26.3%,56.5%,50.0%。Bis （2,6,7-trioxa-1-phosphabicyclo [ 2. 2. 2 ] octane-4-methanol ） chlorophosphate （ intermediate Ⅰ） and tris（2,6,7-trioxa-1-phosphabicyclo [ 2. 2. 2 ] octane-4-methanol ） phosphate （ d ） were synthesized from 1-oxo-4-hydroxymethyl-2,6,7-trioxa-l-phosphabicyclo [ 2. 2. 2 ] octane （ PEPA ） and phosphorus oxychloride in molar ratios 2：1 and 3：1 respectively with the yields of 84. 7% and 80%. The reaction of intermediate Ⅰ with tribromophenol, pentabromobenzyl bromide and melamine respectively gave three other caged phosphates （a -c） in the yields of 70% ,73.5% and 81%. All the title compounds were confirmed by FTIR, ^1HNMR and elementary analysis. Reaction conditions were also discussed. The result of thermal analysis showed that they all have high thermal stability and excellent char-forming ability, decomposition temperatures of compound a - d were 285,325,320 and 337℃, respectively, and residual carbon （ω%） under 500℃ were 38.4% ,26.3% ,56.5% and 50.0% ,respectively.

关 键 词：笼状磷酸酯 PEPA 膨胀型阻燃剂 

分 类 号：TQ314.248[化学工程—高聚物工业]